Processes for producing epsilon caprolactones and/or hydrates and/or esters thereof

ABSTRACT

This invention relates in part to processes for producing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof which comprise subjecting one or more substituted or unsubstituted penten-1-ols to carbonylation in the presence of a carbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof. The substituted and unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactam. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof as principal product(s) of reaction.

BRIEF SUMMARY OF THE INVENTION

1 TECHNICAL FIELD

This invention relates in part to processes for selectively producingone or more substituted or unsubstituted epsilon caprolactones and/orhydrates and/or esters thereof or reaction mixtures containing one ormore substituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. This invention also relates in part to reactionmixtures containing one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates and/or esters thereof as the desiredproduct(s) of reaction.

2 BACKGROUND OF THE INVENTION

Epsilon caprolactone and/or certain hydrates and/or certain estersthereof are valuable intermediates which are useful, for example, in theproduction of epsilon caprolactam and polyesters. The processescurrently used to produce epsilon caprolactone and/or hydrates and/oresters thereof have various disadvantages. For example, the startingmaterials used to produce epsilon caprolactone and/or hydrates and/oresters thereof are relatively expensive. Accordingly, it would bedesirable to produce epsilon caprolactone and/or hydrates and/or estersthereof from relatively inexpensive starting materials and by a processwhich does not have the disadvantages of prior art processes.

3 DISCLOSURE OF THE INVENTION

It has been discovered that alcohols possessing internal olefinicunsaturation can be converted to epsilon caprolactones and/or hydratesand/or esters thereof In particular, it has been surprisingly discoveredthat penten-1-ols, e.g., 3-penten-1-ols, can be converted to epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof by employing catalysts having carbonylation/isomerizationcapabilities.

This invention relates to processes for producing one or moresubstituted or unsubstituted epsilon caprolactones, e.g., epsiloncaprolactone, and/or hydrates and/or esters thereof which comprisesubjecting one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce said one ormore substituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof.

This invention also relates to processes for producing one or moresubstituted or unsubstituted epsilon caprolactones, e.g., epsiloncaprolactone, and/or hydrates and/or esters thereof which comprise: (a)subjecting one or more substituted or unsubstituted alkadienes, e.g.,butadiene, to hydrocarbonylation in the presence of a hydrocarbonylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce one or more substituted or unsubstituted penten-1-ols; and (b)subjecting said one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce said one ormore substituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. The hydrocarbonylation reaction conditions instep (a) and the carbonylation reaction conditions in step (b) may bethe same or different. The hydrocarbonylation catalyst in step (a) andthe carbonylation catalyst in step (b) may be the same or different.

This invention further relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted epsilon caprolactones,e.g., epsilon caprolactone, and/or hydrates thereof, e.g.,6-hydroxyhexanoic acid, and/or esters thereof, e.g., 6-hydroxyhexanoicacid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

(2) one or more substituted or unsubstituted penten-1-ols, e.g.,cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

(4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal; and

(6) optionally one or more substituted or unsubstituted valeraldehydes;

wherein the weight ratio of component (1) to the sum of components (3),(4), (5) and (6) is greater than about 0.1, preferably greater thanabout 0.25, more preferably greater than about 1.0; and the weight ratioof component (2) to the sum of components (1), (3), (4), (5), and (6) isabout 0 to about 100, preferably about 0.001 to about 50; which processcomprises subjecting one or more substituted or unsubstitutedpenten-1-ols to carbonylation in the presence of a carbonylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce said batchwise or continuously generated reaction mixture.

This invention yet further relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted epsilon caprolactones,e.g., epsilon caprolactone, and/or hydrates thereof, e.g.,6-hydroxyhexanoic acid, and/or esters thereof, e.g., 6-hydroxyhexanoicacid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

(4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(6) optionally one or more substituted or unsubstituted pentan-1-ols;

(7) optionally one or more substituted or unsubstituted valeraldehydes;

(8) optionally one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

(9) optionally one or more substituted or unsubstituted 1,6-hexanedials,e.g., adipaldehyde;

(10) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

(11) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

(12) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5), (6), (7), (8), (9), (10) and (11) is greater than about0.1, preferably greater than about 0.25, more preferably greater thanabout 1.0; and the weight ratio of component (12) to the sum ofcomponents (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) isabout 0 to about 100, preferably about 0.001 to about 50;

which process comprises: (a) subjecting one or more substituted orunsubstituted butadienes, e.g., butadiene, to hydrocarbonylation in thepresence of a hydrocarbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce one or moresubstituted or unsubstituted penten-1-ols; and (b) subjecting said oneor more substituted or unsubstituted penten-1-ols to carbonylation inthe presence of a carbonylation catalyst, e.g., a metal-organophosphorusligand complex catalyst, to produce said batchwise or continuouslygenerated reaction mixture. The hydrocarbonylation reaction conditionsin step (a) and the carbonylation reaction conditions in step (b) may bethe same or different. The hydrocarbonylation catalyst in step (a) andthe carbonylation catalyst in step (b) may be the same or different.

This invention also relates to a process for producing a reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof which process comprises subjecting one or more substituted orunsubstituted penten-1-ols to carbonylation in the presence of acarbonylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce said reaction mixture comprising one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof.

This invention further relates to a process for producing a reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof which process comprises: (a) subjecting one or more substitutedor unsubstituted alkadienes, e.g., butadiene, to hydrocarbonylation inthe presence of a hydrocarbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce one or moresubstituted or unsubstituted penten-1-ols; and (b) subjecting said oneor more substituted or unsubstituted penten-1-ols to carbonylation inthe presence of a carbonylation catalyst, e.g., a metal-organophosphorusligand complex catalyst, to produce said reaction mixture comprising oneor more substituted or unsubstituted epsilon caprolactones and/orhydrates and/or esters thereof. The hydrocarbonylation reactionconditions in step (a) and the carbonylation reaction conditions in step(b) may be the same or different. The hydrocarbonylation catalyst instep (a) and the carbonylation catalyst in step (b) may be the same ordifferent.

The processes of this invention can achieve high selectivities ofalkadienes and penten-1-ols to epsilon caprolactones and/or hydratesand/or esters thereof, i.e., selectivities of alkadienes to epsiloncaprolactones and/or hydrates and/or esters thereof of at least 10% byweight and up to 85% by weight or greater may be achieved by theprocesses of this invention.

This invention yet further relates in part to a batchwise orcontinuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted epsilon caprolactones,e.g., epsilon caprolactone, and/or hydrates thereof, e.g.,6-hydroxyhexanoic acid, and/or esters thereof, e.g., 6-hydroxyhexanoicacid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

(2) one or more substituted or unsubstituted penten-1-ols, e.g.,cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

(4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal; and

(6) optionally one or more substituted or unsubstituted valeraldehydes;

wherein the weight ratio of component (1) to the sum of components (3),(4), (5) and (6) is greater than about 0.1, preferably greater thanabout 0.25, more preferably greater than about 1.0; and the weight ratioof component (2) to the sum of components (1), (3), (4), (5), and (6) isabout 0 to about 100, preferably about 0.001 to about 50.

This invention also relates in part to a batchwise or continuouslygenerated reaction mixture comprising:

(1) one or more substituted or unsubstituted epsilon caprolactones,e.g., epsilon caprolactone, and/or hydrates thereof, e.g.,6-hydroxyhexanoic acid, and/or esters thereof, e.g., 6-hydroxyhexanoicacid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

(4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(6) optionally one or more substituted or unsubstituted pentan-1-ols;

(7) optionally one or more substituted or unsubstituted valeraldehydes;

(8) optionally one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

(9) optionally one or more substituted or unsubstituted 1,6-hexanedials,e.g., adipaldehyde;

(10) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

(11) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

(12) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5), (6), (7), (8), (9), (10) and (11) is greater than about0.1, preferably greater than about 0.25, more preferably greater thanabout 1.0; and the weight ratio of component (12) to the sum ofcomponents (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) isabout 0 to about 100, preferably about 0.001 to about 50.

This invention further relates in part to a reaction mixture comprisingone or more substituted or unsubstituted epsilon caprolactones, e.g.,epsilon caprolactone, and/or hydrates and/or esters thereof in whichsaid reaction mixture is prepared by a process which comprisessubjecting one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst,metal-organophosphorus ligand complex catalyst, to produce said reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates and/or esters thereof.

This invention yet further relates in part to a reaction mixturecomprising one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof in which said reaction mixture is prepared by a process whichcomprises: (a) subjecting one or more substituted or unsubstitutedalkadienes, e.g., butadiene, to hydrocarbonylation in the presence of ahydrocarbonylation catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, to produce one or more substituted or unsubstitutedpenten-1-ols; and (b) subjecting said one or more substituted orunsubstituted penten-1-ols to carbonylation in the presence of acarbonylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce said reaction mixture comprising one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. The hydrocarbonylation reaction conditions instep (a) and the carbonylation reaction conditions in step (b) may bethe same or different. The hydrocarbonylation catalyst in step (a) andthe carbonylation catalyst in step (b) may be the same or different.

The reaction mixtures of this invention are distinctive insofar as theprocesses for their preparation achieve the generation of highselectivities of epsilon caprolactones and/or hydrates and/or estersthereof in a manner which can be suitably employed in a commercialprocess for the manufacture of epsilon caprolactones and/or hydratesand/or esters thereof. In particular, the reaction mixtures of thisinvention are distinctive insofar as the processes for their preparationallow for the production of epsilon caprolactones and/or hydrates and/oresters thereof in relatively high yields without generating largeamounts of byproducts, e.g., methyl valerolactone.

DETAILED DESCRIPTION

Hydrocarbonylation Step or Stage

The hydrocarbonylation stage or step involves converting one or moresubstituted or unsubstituted alkadienes to one or more substituted orunsubstituted unsaturated alcohols. The hydrocarbonylation stage or stepmay be conducted in one or more steps or stages, preferably a one stepprocess. As used herein, the term “hydrocarbonylation” is contemplatedto include all permissible hydrocarbonylation processes which involveconverting one or more substituted or unsubstituted alkadienes to one ormore substituted or unsubstituted unsaturated alcohols. In general, thehydrocarbonylation step or stage comprises reacting one or moresubstituted or unsubstituted alkadienes, e.g., butadienes, with carbonmonoxide and hydrogen in the presence of a metal-ligand complexcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, and apromoter and optionally free ligand to produce one or more substitutedor unsubstituted unsaturated alcohols, e.g., penten-1-ols. A preferredhydrocarbonylation process useful in this invention is disclosed in U.S.patent application Ser. No. 08/843,381, filed on an even date herewith,the disclosure of which is incorporated herein by reference.

The hydrocarbonylation stage or step involves the production ofunsaturated alcohols by reacting an alkadiene with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst andoptionally free ligand in a liquid medium that also contains a promoter.The reaction may be carried out in a continuous single pass mode in acontinuous gas recycle manner or more preferably in a continuous liquidcatalyst recycle manner as described below. The hydrocarbonylationprocessing techniques employable herein may correspond to any knownprocessing techniques.

The hydrocarbonylation process mixtures employable herein includes anysolution derived from any corresponding hydrocarbonylation process thatmay contain at least some amount of four different main ingredients orcomponents, i.e., the unsaturated alcohol product, a metal-ligandcomplex catalyst, a promoter and optionally free ligand, saidingredients corresponding to those employed and/or produced by thehydrocarbonylation process from whence the hydrocarbonylation processmixture starting material may be derived. By “free ligand” is meantligand that is not complexed with (tied to or bound to) the metal, e.g.,rhodium atom, of the complex catalyst. It is to be understood that thehydrocarbonylation process mixture compositions employable herein canand normally will contain minor amounts of additional ingredients suchas those which have either been deliberately employed in thehydrocarbonylation process or formed in situ during said process.Examples of such ingredients that can also be present include unreactedalkadiene starting material, carbon monoxide and hydrogen gases, and insitu formed type products, such as saturated alcohols and/or unreactedisomerized olefins corresponding to the alkadiene starting materials,and high boiling liquid byproducts, as well as other inert co-solventtype materials or hydrocarbon additives, if employed.

The catalysts useful in the hydrocarbonylation stage or step includemetal-ligand complex catalysts. The permissible metals which make up themetal-ligand complexes include Group 8, 9 and 10 metals selected fromrhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe),nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixturesthereof, with the preferred metals being rhodium, cobalt, iridium andruthenium, more preferably rhodium, cobalt and ruthenium, especiallyrhodium. The permissible ligands include, for example, organophosphorus,organoarsenic and organoantimony ligands, or mixtures thereof,preferably organophosphorus ligands. The permissible organophosphorusligands which make up the metal-organophosphorus ligand complexes andfree organophosphorus ligand include mono-, di-, tri- and higherpoly-(organophosphorus) compounds, preferably those of high basicity andlow steric bulk. Illustrative permissible organophosphorus ligandsinclude, for example, organophosphines, organophosphites,organophosphonites, organophosphinites, organophosphorusnitrogen-containing ligands, organophosphorus sulfur-containing ligands,organophosphorus silicon-containing ligands and the like. Otherpermissible ligands include, for example, heteroatom-containing ligandssuch as described in U.S. patent application Ser. No. 08/818,781, filedMar. 10, 1997, the disclosure of which is incorporated herein byreference. Mixtures of such ligands may be employed if desired in themetal-ligand complex catalyst and/or free ligand and such mixtures maybe the same or different. It is to be noted that the successful practiceof this invention does not depend and is not predicated on the exactstructure of the metal-ligand complex species, which may be present intheir mononuclear, dinuclear and/or higher nuclearity forms. Indeed, theexact structure is not known. Although it is not intended herein to bebound to any theory or mechanistic discourse, it appears that thecatalytic species may in its simplest form consist essentially of themetal in complex combination with the ligand and carbon monoxide whenused.

The term “complex” as used herein and in the claims means a coordinationcompound formed by the union of one or more electronically richmolecules or atoms capable of independent existence with one or moreelectronically poor molecules or atoms, each of which is also capable ofindependent existence. For example, the ligands employable herein, i.e.,organophosphorus ligands, may possess one or more phosphorus donoratoms, each having one available or unshared pair of electrons which areeach capable of forming a coordinate covalent bond independently orpossibly in concert (e.g., via chelation) with the metal. Carbonmonoxide (which is also properly classified as a ligand) can also bepresent and complexed with the metal. The ultimate composition of thecomplex catalyst may also contain an additional ligand, e.g., hydrogenor an anion satisfying the coordination sites or nuclear charge of themetal. Illustrative additional ligands include, e.g., halogen (Cl, Br,I), alkyl, aryl, substituted aryl, acyl, CF₃, C₂F₅, CN, (R)₂PO andRP(O)(OH)O (wherein each R is the same or different and is a substitutedor unsubstituted hydrocarbon radical, e.g., the alkyl or aryl), acetate,acetylacetonate, SO₄, BF₄, PF₆, NO₂, NO₃, CH₃O, CH₂═CHCH₂, CH₃CH═CHCH₂,C₆H₅CN, CH₃CN, NO, NH₃, pyridine, (C₂H₅)₃N, mono-olefins, diolefins andtriolefins, tetrahydrofuran, and the like. It is of course to beunderstood that the complex species are preferably free of anyadditional organic ligand or anion that might poison the catalyst andhave an undue adverse effect on catalyst performance. It is preferred inthe metal-ligand complex catalyzed hydrocarbonylation processes that theactive catalysts be free of halogen and sulfur directly bonded to themetal, although such may not be absolutely necessary. Preferredmetal-ligand complex catalysts include rhodium-organophosphine ligandcomplex catalysts.

The number of available coordination sites on such metals is well knownin the art. Thus the catalytic species may comprise a complex catalystmixture, in their monomeric, dimeric or higher nuclearity forms, whichare preferably characterized by at least one phosphorus-containingmolecule complexed per metal, e.g., rhodium. As noted above, it isconsidered that the catalytic species of the preferred catalyst employedin the hydrocarbonylation stage or step may be complexed with carbonmonoxide and hydrogen in addition to the organophosphorus ligands inview of the carbon monoxide and hydrogen gas employed by thehydrocarbonylation stage or step.

Among the organophosphines that may serve as the ligand of themetal-organophosphine complex catalyst and/or free organophosphineligand of the hydrocarbonylation process mixture starting materials aremono-, di-, tri- and poly-(organophosphines) such astriorganophosphines, trialkylphosphines, alkyldiarylphosphines,dialkylarylphosphines, dicycloalkylarylphosphines,cycloalkyldiarylphosphines, triaralkylphosphines,tricycloalkylphosphines, and triarylphosphines, alkyl and/or aryldiphosphines and bisphosphine mono oxides, as well as ionictriorganophosphines containing at least one ionic moiety selected fromthe salts of sulfonic acid, of carboxylic acid, of phosphonic acid andof quaternary ammonium compounds, and the like. Of course any of thehydrocarbon radicals of such tertiary non-ionic and ionicorganophosphines may be substituted if desired, with any suitablesubstituent that does not unduly adversely affect the desired result ofthe hydrocarbonylation process. The organophosphine ligands employablein the hydrocarbonylation stage or step and/or methods for theirpreparation are known in the art.

Illustrative triorganophosphine ligands may be represented by theformula:

wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical, e.g., an alkyl, cycloalkylor aryl radical. In a preferred embodiment, each R¹ is the same ordifferent and is selected from primary alkyl, secondary alkyl, tertiaryalkyl and aryl. Suitable hydrocarbon radicals may contain from 1 to 24carbon atoms or greater. Illustrative substituent groups that may bepresent on the hydrocarbon radicals include, e.g., substituted orunsubstituted alkyl radicals, substituted or unsubstituted alkoxyradicals, substituted or unsubstituted silyl radicals such as —Si(R²)₃;amino radicals such as —N(R²)₂; acyl radicals such as —C(O)R²; carboxyradicals such as —C(O)OR²; acyloxy radicals such as —OC(O)R²; amidoradicals such as —C(O)N(R²)₂ and —N(R²)C(O)R²; ionic radicals such as—SO₃M wherein M represents inorganic or organic cationic atoms orradicals; sulfonyl radicals such as —SO₂R²; ether radicals such as —OR²;sulfinyl radicals such as —SOR²; selenyl radicals such as —SeR²;sulfenyl radicals such as —SR² as well as halogen, nitro, cyano,trifluoromethyl and hydroxy radicals, and the like, wherein each R²individually represents the same or different substituted orunsubstituted monovalent hydrocarbon radical, with the proviso that inamino substituents such as —N(R²)₂, each R² taken together can alsorepresent a divalent bridging group that forms a heterocyclic radicalwith the nitrogen atom and in amido substituents such as C(O)N(R²)₂ and—N(R²)C(O)R² each —R² bonded to N can also be hydrogen. Illustrativealkyl radicals include, e.g., methyl, ethyl, propyl, butyl, octyl,cyclohexyl, isopropyl and the like. Illustrative aryl radicals include,e.g., phenyl, naphthyl, fluorophenyl, difluorophenyl, benzoyloxyphenyl,carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl,hydroxyphenyl; carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl,acetamidophenyl, dimethylcarbamylphenyl, tolyl, xylyl,4-dimethylaminophenyl, 2,4,6-trimethoxyphenyl and the like.

Illustrative specific organophosphines include, e.g.,trimethylphosphine, triethylphosphine, tributylphosphine,trioctylphosphine, diethylbutylphosphine, diethyl-n-propylphosphine,diethylisopropylphosphine, diethylbenzylphosphine,diethylcyclopentylphosphine, diethylcyclohexylphosphine,triphenylphosphine, tris-p-tolylphosphine,tris-p-methoxyphenylphosphine, tris-dimethylaminophenylphosphine,propyldiphenylphosphine, t-butyldiphenylphosphine,n-butyldiphenylphosphine, n-hexyldiphenylphosphine,cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,tricyclohexylphosphine, tribenzylphosphine, DIOP, i.e.,(4R,5R)-(−)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,and/or (4S,5S )-(+)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane and/or(4S,5R)-(−)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,substituted or unsubstituted bicyclic bisphosphines such as1,2-bis(1,4-cyclooctylenephosphino)ethane,1,3-bis(1,4-cyclooctylenephosphino)propane,1,3-bis(1,5-cyclooctylenephosphino)propane and1,2-bis(2,6-dimethyl-1,4-cyclooctylenephosphino)ethane, substituted orunsubstituted bis(2,2′-diphenylphosphinomethyl)biphenyl such asbis(2,2′-diphenylphosphinomethyl)biphenyl andbis{2,2′-di(4-fluorophenyl)phosphinomethyl}biphenyl, MeC(CH₂PPh₂)₃(triphos), NaO₃S(C₆H₄)CH₂C(CH₂PPh₂)₃ (sulphos),bis(diphenylphosphino)ferrocene, bis(diisopropylphosphino)ferrocene,bis(diphenylphosphino)ruthenocene, as well as the alkali and alkalineearth metal salts of sulfonated triphenylphosphines, e.g., of(tri-m-sulfophenyl)phosphine and of (m-sulfophenyl)diphenyl-phosphineand the like.

The preferred organophosphorus ligands which make up themetal-organophosphorus ligand complex catalysts and freeorganophosphorus ligands are high basicity ligands. In general, thebasicity of the organophosphorus ligands should be greater than or equalto the basicity of triphenylphosphine (pKb of 2.74), e.g., from about2.74 to about 15. Suitable organophosphorus ligands have a pKb of about3 or greater, preferably a pKb of about 3 to about 12, and morepreferably a pKb of about 5 to about 12. pKb values for illustrativeorganophosphorus ligands useful in this invention are given in the TableI below. In addition, the organophosphorus ligands useful in thisinvention have a steric bulk sufficient to promote thehydrocarbonylation reaction. The steric bulk of monodentateorganophosphorus ligands should be lower than or equal to a Tolman coneangle of 210°, preferably lower than or equal to the steric bulk oftricyclohexylphosphine (Tolman cone angle=170°). Organophosphorusligands having desired basicity and steric bulk include, for example,substituted or unsubstituted tri-primary-alkylphosphines (e.g.,trioctylphosphine, diethylbutylphosphine, diethylisobutylphosphine),di-primary-alkylarylphosphines (e.g., diethylphenylphosphine,diethyl-p-N,N-dimethylphenylphosphine),di-primary-alkyl-mono-secondary-alkylphosphines (e.g.,diethylisopropylphosphine, diethylcyclohexylphosphine),di-primary-alkyl-tert-alkylphosphines (e.g.,diethyl-tert-butylphosphine), mono-primary-alkyl-diarylphosphines (e.g.,diphenylmethylphosphine),mono-primary-alkyl-di-secondary-alkylphosphines (e.g.,dicyclohexylethylphosphine), triarylphosphines (e.g.,tri-para-N,N-dimethylaminophenylphosphine),tri-secondarylalkylphosphines (e.g., tricyclohexylphosphine),mono-primaryalkyl-mono-secondaryalkyl-mono-tertiary alkylphosphines(e.g., ethylisopropyltert-butylphosphine) and the like. The permissibleorganophosphorus ligands may be substituted with any suitablefunctionalities and may include the promoter as described hereinbelow.

TABLE I Organophosphorus Ligand pKb Trimethylphosphine 8.7Triethylphosphine 8.7 Tri-n-propylphosphine 8.7 Tri-n-butylphosphine 8.4Tri-n-octylphosphine 8.4 Tri-tert-butylphosphine 11.4Diethyl-tert-butylphosphine 10.1 Tricyclohexylphosphine 10Diphenylmethylphosphine 4.5 Diethylphenylphosphine 6.4Diphenylcyclohexylphosphine 5 Diphenylethylphosphine 4.9Tri(p-methoxyphenyl)phosphine 4.6 Triphenylphosphine 2.74Tri(p-N,N-dimethylaminophenyl)phosphine 8.65Tri(p-methylphenyl)phosphine 3.84

More particularly, illustrative metal-organophosphine complex catalystsand illustrative free organophosphine ligands include, for example,those disclosed in U.S. Pat. Nos. 3,239,566, 3,527,809; 4,148,830;4,247,486; 4,283,562; 4,400,548; 4,482,749 and 4,861,918, thedisclosures of which are incorporated herein by reference.

Other illustrative permissible organophosphorus ligands which may makeup the metal-organophosphorus ligand complexes and free organophosphorusligands include, for example, those disclosed in U.S. Pat. Nos.4,567,306, 4,599,206, 4,668,651, 4,717,775, 3,415,906, 4,567,306,4,599,206, 4,748,261, 4,769,498, 4,717,775, 4,885,401, 5,202,297,5,235,113, 5,254,741, 5,264,616, 5,312,996, 5,364,950, 5,391,801, U.S.patent application Ser. No. 08/753,505, filed Nov. 26, 1996, and U.S.patent application Ser. No. 08/843,389, filed on an even date herewith,the disclosures of which are incorporated herein by reference.

The metal-ligand complex catalysts employable in this invention may beformed by methods known in the art. The metal-ligand complex catalystsmay be in homogeneous or heterogeneous form. For instance, preformedmetal hydrido-carbonyl-organophosphorus ligand catalysts may be preparedand introduced into the reaction mixture of a hydrocarbonylationprocess. More preferably, the metal-ligand complex catalysts can bederived from a metal catalyst precursor which may be introduced into thereaction medium for in situ formation of the active catalyst. Forexample, rhodium catalyst precursors such as rhodium dicarbonylacetylacetonate, Rh₂O₃, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Rh(NO₃)₃ and the like maybe introduced into the reaction mixture along with the organophosphorusligand for the in situ formation of the active catalyst. In a preferredembodiment of this invention, rhodium dicarbonyl acetylacetonate isemployed as a rhodium precursor and reacted in the presence of apromoter with the organophosphine ligand to form a catalyticrhodium-organophosphine ligand complex precursor which is introducedinto the reactor along with excess free organophosphine ligand for thein situ formation of the active catalyst. In any event, it is sufficientfor the purpose of this invention that carbon monoxide, hydrogen andorganophosphorus compound are all ligands that are capable of beingcomplexed with the metal and that an active metal-organophosphorusligand catalyst is present in the reaction mixture under the conditionsused in the hydrocarbonylation process.

More particularly, a catalyst precursor composition can be formedconsisting essentially of a solubilized metal-ligand complex precursorcatalyst, a promoter and free ligand. Such precursor compositions may beprepared by forming a solution of a metal starting material, such as ametal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or maynot be in complex combination with an organophosphorus ligand as definedherein. Any suitable metal starting material may be employed, e.g.rhodium dicarbonyl acetylacetonate, Rh₂O₃, Rh₄(CO)₁₂, Rh₆(CO)₁₆,Rh(NO₃)₃, and organophosphorus ligand rhodium carbonyl hydrides.Carbonyl and organophosphorus ligands, if not already complexed with theinitial metal, may be complexed to the metal either prior to or in situduring the hydrocarbonylation process.

By way of illustration, the preferred catalyst precursor composition ofthis invention consists essentially of a solubilized rhodium carbonylorganophosphine ligand complex precursor catalyst, a promoter and freeorganophosphine ligand prepared by forming a solution of rhodiumdicarbonyl acetylacetonate, a promoter and an organophosphine ligand asdefined herein. The organophosphine ligand readily replaces one of thecarbonyl ligands of the rhodium acetylacetonate complex precursor atroom temperature as witnessed by the evolution of carbon monoxide gas.This substitution reaction may be facilitated by heating the solution ifdesired. Any suitable organic solvent in which both the rhodiumdicarbonyl acetylacetonate complex precursor and rhodium organophosphineligand complex precursor are soluble can be employed. The amounts ofrhodium complex catalyst precursor, organic solvent and organophosphineligand, as well as their preferred embodiments present in such catalystprecursor compositions may obviously correspond to those amountsemployable in the hydrocarbonylation stage or step. Experience has shownthat the acetylacetonate ligand of the precursor catalyst is replacedafter the hydrocarbonylation process has begun with a different ligand,e.g., hydrogen, carbon monoxide or organophosphine ligand, to form theactive complex catalyst as explained above. In a continuous process, theacetylacetone which is freed from the precursor catalyst underhydrocarbonylation conditions is removed from the reaction medium withthe product alcohol and thus is in no way detrimental to thehydrocarbonylation process. The use of such preferred rhodium complexcatalytic precursor compositions provides a simple economical andefficient method for handling the rhodium precursor metal andhydrocarbonylation start-up.

Accordingly, the metal-ligand complex catalysts used in the process ofthis invention consists essentially of the metal complexed with carbonmonoxide and a ligand, said ligand being bonded (complexed) to the metalin a chelated and/or non-chelated fashion. Moreover, the terminology“consists essentially of”, as used herein, does not exclude, but ratherincludes, hydrogen complexed with the metal, in addition to carbonmonoxide and the ligand. Further, such terminology does not exclude thepossibility of other organic ligands and/or anions that might also becomplexed with the metal. Materials in amounts which unduly adverselypoison or unduly deactivate the catalyst are not desirable and so thecatalyst most desirably is free of contaminants such as metal-boundhalogen (e.g., chlorine, and the like) although such may not beabsolutely necessary. The hydrogen and/or carbonyl ligands of an activemetal-organophosphine ligand complex catalyst may be present as a resultof being ligands bound to a precursor catalyst and/or as a result of insitu formation, e.g., due to the hydrogen and carbon monoxide gasesemployed in hydrocarbonylation stage or step.

As noted the hydrocarbonylation process involves the use of ametal-ligand complex catalyst as described herein. Of course mixtures ofsuch catalysts can also be employed if desired. The amount ofmetal-ligand complex catalyst present in the reaction medium of a givenhydrocarbonylation process need only be that minimum amount necessary toprovide the given metal concentration desired to be employed and whichwill furnish the basis for at least the catalytic amount of metalnecessary to catalyze the particular hydrocarbonylation process involvedsuch as disclosed, for example, in the above-mentioned patents. Ingeneral, the catalyst concentration can range from several parts permillion to several percent by weight. Organophosphorus ligands can beemployed in the above-mentioned catalysts in a molar ratio of generallyfrom about 0.5:1 or less to about 1000:1 or greater. The catalystconcentration will be dependent on the hydrocarbonylation processconditions and solvent employed.

In general, the organophosphorus ligand concentration inhydrocarbonylation process mixtures may range from between about 0.005and 25 weight percent based on the total weight of the reaction mixture.Preferably the ligand concentration is between 0.01 and 15 weightpercent, and more preferably is between about 0.05 and 10 weight percenton that basis.

In general, the concentration of the metal in the hydrocarbonylationprocess mixtures may be as high as about 2000 parts per million byweight or greater based on the weight of the reaction mixture.Preferably the metal concentration is between about 50 and 1500 partsper million by weight based on the weight of the reaction mixture, andmore preferably is between about 70 and 1200 parts per million by weightbased on the weight of the reaction mixture.

In addition to the metal-ligand complex catalyst, free ligand (i.e.,ligand that is not complexed with the rhodium metal) may also be presentin the hydrocarbonylation process medium. The free ligand may correspondto any of the above-defined ligands discussed above as employableherein. It is preferred that the free ligand be the same as the ligandof the metal-ligand complex catalyst employed. However, such ligandsneed not be the same in any given process. The hydrocarbonylationprocess may involve up to 100 moles, or higher, of free ligand per moleof metal in the hydrocarbonylation process medium. Preferably thehydrocarbonylation process is carried out in the presence of from about1 to about 50 moles of coordinatable phosphorus, more preferably fromabout 1 to about 20 moles of coordinatable phosphorus, and mostpreferably from about 1 to about 8 moles of coordinatable phosphorus,per mole of metal present in the reaction medium; said amounts ofcoordinatable phosphorus being the sum of both the amount ofcoordinatable phosphorus that is bound (complexed) to the rhodium metalpresent and the amount of free (non-complexed) coordinatable phosphoruspresent. Of course, if desired, make-up or additional coordinatablephosphorus can be supplied to the reaction medium of thehydrocarbonylation process at any time and in any suitable manner, e.g.to maintain a predetermined level of free ligand in the reaction medium.

As indicated above, the hydrocarbonylation catalyst may be inheterogeneous form during the reaction and/or during the productseparation. Such catalysts are particularly advantageous in thehydrocarbonylation of alkadienes to produce high boiling or thermallysensitive alcohols, so that the catalyst may be separated from theproducts by filtration or decantation at low temperatures. For example,the rhodium catalyst may be attached to a support so that the catalystretains its solid form during both the hydrocarbonylation and separationstages, or is soluble in a liquid reaction medium at high temperaturesand then is precipitated on cooling.

As an illustration, the rhodium catalyst may be impregnated onto anysolid support. such as inorganic oxides, (e.g., alumina, silica,titania, or zirconia) carbon, or ion exchange resins. The catalyst maybe supported on, or intercalated inside the pores of, a zeolite orglass; the catalyst may also be dissolved in a liquid film coating thepores of said zeolite or glass. Such zeolite-supported catalysts areparticularly advantageous for producing one or more regioisomericalcohols in high selectivity, as determined by the pore size of thezeolite. The techniques for supporting catalysts on solids, such asincipient wetness, which will be known to those skilled in the art. Thesolid catalyst thus formed may still be complexed with one or more ofthe ligands defined above. Descriptions of such solid catalysts may befound in for example: J. Mol. Cat. 1991, 70, 363-368; Catal. Lett. 1991,8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339,454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.

The rhodium catalyst may be attached to a thin film or membrane support,such as cellulose acetate or polyphenylenesulfone, as described in forexample J. Mol. Cat. 1990, 63, 213-221.

The rhodium catalyst may be attached to an insoluble polymeric supportthrough an organophosphorus-containing ligand, such as a phosphine orphosphite, incorporated into the polymer. Such polymer-supported ligandsare well known, and include such commercially available species as thedivinylbenzene/polystyrene-supported triphenylphosphine. The supportedligand is not limited by the choice of polymer or phosphorus-containingspecies incorporated into it. Descriptions of polymer-supportedcatalysts may be found in for example: J. Mol. Cat. 1993, 83, 17-35;Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127.

In the heterogeneous catalysts described above, the catalyst may remainin its heterogeneous form during the entire hydrocarbonylation andcatalyst separation process. In another embodiment of the invention, thecatalyst may be supported on a polymer which, by the nature of itsmolecular weight, is soluble in the reaction medium at elevatedtemperatures, but precipitates upon cooling, thus facilitating catalystseparation from the reaction mixture. Such “soluble” polymer-supportedcatalysts are described in for example: Polymer, 1992, 33, 161; J. Org.Chem. 1989, 54, 2726-2730.

When the rhodium catalyst is in a heterogeneous or supported form, thereaction may be carried out in the gas phase. More preferably, thereaction is carried out in the slurry phase due to the high boilingpoints of the products, and to avoid decomposition of the productalcohols. The catalyst may then be separated from the product mixture byfiltration or decantation.

The processes of this invention can be operated over a wide range ofreaction rates (m/L/h=moles of product/liter of reaction solution/hour).Typically, the reaction rates are at least 0.01 m/L/h or higher,preferably at least 0.1 m/L/h or higher, and more preferably at least0.5 m/L/h or higher. Higher reaction rates are generally preferred froman economic standpoint, e.g., smaller reactor size, etc.

The substituted and unsubstituted alkadiene starting materials useful inthe hydrocarbonylation stage or step include, but are not limited to,conjugated aliphatic diolefins represented by the formula:

wherein R₁ and R₂ are the same or different and are hydrogen, halogen ora substituted or unsubstituted hydrocarbon radical. The alkadienes canbe linear or branched and can contain substituents (e.g., alkyl groups,halogen atoms, amino groups or silyl groups). Illustrative of suitablealkadiene starting materials are butadiene, isoprene, dimethylbutadiene, cyclopentadiene and chloroprene. Most preferably, thealkadiene starting material is butadiene itself (CH₂═CH—CH═CH₂). Forpurposes of this invention, the term “alkadiene” is contemplated toinclude all permissible substituted and unsubstituted conjugateddiolefins, including all permissible mixtures comprising one or moresubstituted and unsubstituted conjugated diolefins. Illustrative ofsuitable substituted and unsubstituted alkadienes (including derivativesof alkadienes) include those permissible substituted and unsubstitutedalkadienes described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, 1996, the pertinent portions of which areincorporated herein by reference.

The particular hydrocarbonylation reaction conditions are not narrowlycritical and can be any effective hydrocarbonylation proceduressufficient to produce one or more unsaturated alcohols. The exactreaction conditions will be governed by the best compromise betweenachieving high catalyst selectivity, activity, lifetime and ease ofoperability, as well as the intrinsic reactivity of the startingmaterials in question and the stability of the starting materials andthe desired reaction product to the reaction conditions. Thehydrocarbonylation process conditions may include any suitable typehydrocarbonylation conditions heretofore employed for producingalcohols. The total pressure employed in the hydrocarbonylation processmay range in general from about 1 to about 10,000 psia, preferably fromabout 20 to 3000 psia and more preferably from about 50 to about 2000psia. The total pressure of the hydrocarbonylation process will bedependent on the particular catalyst system employed.

More specifically, the carbon monoxide partial pressure of thehydrocarbonylation process in general may range from about 1 to about3000 psia, and preferably from about 3 to about 1500 psia, while thehydrogen partial pressure in general may range from about 1 to about3000 psia, and preferably from about 3 to about 1500 psia. In general,the molar ratio of carbon monoxide to gaseous hydrogen may range fromabout 100:1 or greater to about 1:100 or less, the preferred carbonmonoxide to gaseous hydrogen molar ratio being from about 1:10 to about10:1. The carbon monoxide and hydrogen partial pressures will bedependent in part on the particular catalyst system employed. It isunderstood that carbon monoxide and hydrogen can be employed separately,either alone or in mixture with each other, i.e., synthesis gas, or maybe produced in situ under reaction conditions and/or be derived from thepromoter or solvent (not necessarily involving free hydrogen or carbonmonoxide). In an embodiment, the hydrogen partial pressure and carbonmonoxide partial pressure are sufficient to prevent or minimizederivatization, e.g., hydrogenation of penten-1-ols or furtherhydrocarbonylation of penten-1-ols or hydrogenation of alkadienes.

Further, the hydrocarbonylation process may be conducted at a reactiontemperature from about 20° C. to about 200° C., preferably from about50° C. to about 150° C., and more preferably from about 65° C. to about115° C. The temperature must be sufficient for reaction to occur (whichmay vary with catalyst system employed), but not so high that ligand orcatalyst decomposition occurs. At high temperatures (which may vary withcatalyst system employed), conversion of penten-1-ols to undesiredbyproducts may occur.

Of course, it is to be also understood that the hydrocarbonylationprocess conditions employed will be governed by the type of unsaturatedalcohol product desired.

To enable maximum levels of 3-penten-1-ols and/or 4-penten-1-ols andminimize 2-penten-1-ols, it is desirable to maintain some alkadienepartial pressure or when the alkadiene conversion is complete, thecarbon monoxide and hydrogen partial pressures should be sufficient toprevent or minimize derivatization, e.g., hydrogenation of penten-1-olsor further hydrocarbonylation of penten-1-ols or hydrogenation ofalkadienes.

In a preferred embodiment, the alkadiene hydrocarbonylation is conductedat an alkadiene partial pressure and/or a carbon monoxide and hydrogenpartial pressures sufficient to prevent or minimize derivatization,e.g., hydrogenation of penten-1-ols or further hydrocarbonylation ofpenten-1-ols or hydrogenation of alkadienes. In a more preferredembodiment, the alkadiene, e.g., butadiene, hydrocarbonylation isconducted at an alkadiene partial pressure of greater than 0 psi,preferably greater than 5 psi, and more preferably greater than 9 psi;at a carbon monoxide partial pressure of greater than 0 psi, preferablygreater than 25 psi, and more preferably greater than 40 psi; and at ahydrogen partial pressure of greater than 0 psi, preferably greater than25 psi, and more preferably greater than 80 psi.

The hydrocarbonylation process is also conducted in the presence of apromoter. As used herein, “promoter” means an organic or inorganiccompound with an ionizable hydrogen of pKa of from about 1 to about 35.Illustrative promoters include, for example, protic solvents, organicand inorganic acids, alcohols, water, phenols, thiols, thiophenols,nitroalkanes, ketones, nitriles, amines (e.g., pyrroles anddiphenylamine), amides (e.g., acetamide), mono-, di- andtrialkylammonium salts, and the like. Approximate pKa values forillustrative promoters useful in this invention are given in the TableII below. The promoter may be present in the hydrocarbonylation reactionmixture either alone or incorporated into the ligand structure, eitheras the metal-ligand complex catalyst or as free ligand, or into thealkadiene structure. The desired promoter will depend on the nature ofthe ligands and metal of the metal-ligand complex catalysts. In general,a catalyst with a more basic metal-bound acyl or other intermediate willrequire a lower concentration and/or a less acidic promoter.

Although it is not intended herein to be bound to any theory ormechanistic discourse, it appears that the promoter may function totransfer a hydrogen ion to or otherwise activate a catalyst-bound acylor other intermediate. Mixtures of promoters in any permissiblecombination may be useful in this invention. A preferred class ofpromoters includes those that undergo hydrogen bonding, e.g., NH, OH andSH-containing groups and Lewis acids, since this is believed tofacilitate hydrogen ion transfer to or activation of the metal-boundacyl or other intermediate. In general, the amount of promoter may rangefrom about 10 parts per million or so up to about 99 percent by weightor more based on the total weight of the hydrocarbonylation processmixture starting materials.

TABLE II Promoter pKa ROH (R = alkyl) 15-19 ROH (R = aryl) 8-11 RCONHR(R = hydrogen or alkyl, 15-19 e.g., acetamide) R₃NH⁺, R₂NH₂ ⁺ (R =alkyl) 10-11 RCH₂NO₂ 8-11 RCOCH₂R (R = alkyl) 19-20 RSH (R = alkyl)10-11 RSH (R = aryl) 8-11 CNCH₂CN 11 Diarylamine 21-24 Pyrrole 20Pyrrolidine 34

The concentration of the promoter employed will depend upon the detailsof the catalyst system employed. Without wishing to be bound by theory,the promoter component must be sufficiently acidic and in sufficientconcentration to transfer a hydrogen ion to or otherwise activate thecatalyst-bound acyl or other intermediate. It is believed that apromoter component acidity or concentration which is insufficient totransfer a hydrogen ion to or otherwise activate the catalyst-bound acylor other intermediate will result in the formation of pentenal products,rather than the preferred penten-1-ol products. The ability of apromoter component to transfer a hydrogen ion to or otherwise activatethe catalyst-bound acyl or other intermediate may be governed by severalfactors, for example, the concentration of the promoter component, theintrinsic acidity of the promoter component (the pKa), the compositionof the reaction medium (e.g., the reaction solvent) and the temperature.Promoters are chosen on the basis of their ability to transfer ahydrogen ion to or otherwise activate such a catalyst-bound acyl orother intermediate under reaction conditions sufficient to result in theformation of alcohol products, but not so high as to result indetrimental side reactions of the catalyst, reactants or products. Incases where the promoter component acidity or concentration isinsufficient to do so, aldehyde products (e.g., pentenals) are initiallyformed which may or may not be subsequently converted to unsaturatedalcohols, e.g., penten-1-ols.

In general, a less basic metal-bound acyl will require a higherconcentration of the promoter component or a more acidic promotercomponent to protonate or otherwise activate it fully, such that theproducts are more desired penten-1-ols, rather than pentenals. This canbe achieved by appropriate choice of promoter component. For example, anenabling concentration of protonated or otherwise activatedcatalyst-bound acyl or other intermediate can be achieved though the useof a large concentration of a mildly acidic promoter component, orthrough the use of a smaller concentration of a more acidic component.The promoter component is selected based upon its ability to produce thedesired concentration of protonated or otherwise activatedcatalyst-bound acyl or other intermediate in the reaction medium underreaction conditions. In general, the intrinsic strength of an acidicmaterial is generally defined in aqueous solution as the pKa, and not inreaction media commonly employed in hydrocarbonylation. The choice ofthe promoter and its concentration is made based in part upon thetheoretical or equivalent pH that the promoter alone at suchconcentration gives in aqueous solution at 22° C. The desiredtheoretical or equivalent pH of promoter component solutions should begreater than 0, preferably from about 1-12, more preferably from about2-10 and most preferably from 4-8. The theoretical or equivalent pH canbe readily calculated from values of pKa's at the appropriate promotercomponent concentration by reference to standard tables such as thosefound in “Ionization Constants of Organic Acids in Aqueous Solution”(IUPAC Chemical Data Series—No. 23) by E. P Serjeant and Boyd Dempsey,Pergamon Press (1979) and “Dissociation Constants of Inorganic Acids andBases in Aqueous Solution” (IUPAC Chemical Data Series—No. 19, by D. D.Perrin, Pergamon Press.

Depending on the particular catalyst and reactants employed, suitablepromoters preferably include solvents, for example, alcohols (e.g., theunsaturated alcohol products such as penten-1-ols), thiols, thiophenols,selenols, tellurols, alkenes, alkynes, aldehydes, higher boilingbyproducts, ketones, esters, amides, primary and secondary amines,alkylaromatics and the like. Any suitable promoter which does not undulyadversely interfere with the intended hydrocarbonylation process can beemployed. Permissible protic solvents have a pKa of about 1-35,preferably a pKa of about 3-30, and more preferably a pKa of about 5-25.Mixtures of one or more different solvents may be employed if desired.

In general, with regard to the production of unsaturated alcohols, it ispreferred to employ unsaturated alcohol promoters corresponding to theunsaturated alcohol products desired to be produced and/or higherboiling byproducts as the main protic solvents. Such byproducts can alsobe preformed if desired and used accordingly. Illustrative preferredprotic solvents employable in the production of unsaturated alcohols,e.g., penten-1-ols, include alcohols (e.g., pentenols, octanols,hexanediols), amines, thiols, thiophenols, ketones (e.g. acetone andmethylethyl ketone), hydroxyaldehydes (e.g., 6-hydroxyaldehyde), lactols(e.g., 2-methylvalerolactol), esters (e.g. ethyl acetate), hydrocarbons(e.g. diphenylmethane, triphenylmethane), nitrohydrocarbons (e.g.nitromethane), 1,4-butanediols and sulfolane. Suitable protic solventsare disclosed in U.S. Pat. No. 5,312,996.

As indicated above, the promoter may be incorporated into the ligandstructure, either as the metal-ligand complex catalyst or as freeligand. Suitable ligand promoters which may be useful in this inventioninclude, for example, tris(2-hydroxyethyl)phosphine,tris(3-hydroxypropyl)phosphine, tris(2-hydroxyphenylphosphine),tris(4-hydroxyphenylphosphine), tris(3-carboxypropyl)phosphine,tris(3-carboxamidopropyl)phosphine, diphenyl(2-hydroxyphenyl)phosphine,diethyl(2-anilinophenyl )phosphine, and tris(3-pyrroyl)phosphine. Theuse of ligand promoters may by particularly beneficial in thoseinstances when the unsaturated alcohol product is not effective as apromoter. As with the organophosphorus ligands which make up themetal-organophosphorus ligand complex catalysts and freeorganophosphorus ligands, the organophosphorus ligand promoterspreferably are high basicity ligands having a steric bulk lower than orequal to a Tolman cone angle of 210°, preferably lower than or equal tothe steric bulk of tricyclohexylphosphine (Tolman cone angle=170°).Indeed, the organophosphorus ligand promoters may be employed asorganophosphorus ligands which make up the metal-organophosphorus ligandcomplex catalysts and free organophosphorus ligands. Mixtures ofpromoters comprising one or more ligand promoters and mixturescomprising one or more ligand promoters and one or more other promoters,e.g., protic solvents, may be useful in this invention.

In an embodiment of the invention, the hydrocarbonylation processmixture may consist of one or more liquid phases, e.g. a polar and anonpolar phase. Such processes are often advantageous in, for example,separating products from catalyst and/or reactants by partitioning intoeither phase. In addition, product selectivities dependent upon solventproperties may be increased by carrying out the reaction in thatsolvent. An application of this technology is the aqueous-phasehydrocarbonylation of alkadienes employing sulfonated phosphine ligands,hydroxylated phosphine ligands and aminated phosphine ligands for therhodium catalyst. A process carried out in aqueous solvent isparticularly advantageous for the preparation of alcohols because theproducts may be separated from the catalyst by extraction into asolvent.

As described herein, the phosphorus-containing ligand for the rhodiumhydrocarbonylation catalyst may contain any of a number of substituents,such as cationic or anionic substituents, which will render the catalystsoluble in a polar phase, e.g. water. Optionally, a phase-transfercatalyst may be added to the reaction mixture to facilitate transport ofthe catalyst, reactants, or products into the desired solvent phase. Thestructure of the ligand or the phase-transfer catalyst is not criticaland will depend on the choice of conditions, reaction solvent, anddesired products.

When the catalyst is present in a multiphasic system, the catalyst maybe separated from the reactants and/or products by conventional methodssuch as extraction or decantation. The reaction mixture itself mayconsist of one or more phases; alternatively, the multiphasic system maybe created at the end of the reaction by for example addition of asecond solvent to separate the products from the catalyst. See, forexample, U.S. Pat. No. 5,180,854, the disclosure of which isincorporated herein by reference.

In an embodiment of the process of this invention, an olefin can behydrocarbonylated along with an alkadiene using the above-describedmetal-ligand complex catalysts. In such cases, an alcohol derivative ofthe olefin is also produced along with the unsaturated alcohols, e.g.,penten-1-ols.

Mixtures of different olefinic starting materials can be employed, ifdesired, in the hydrocarbonylation processes. More preferably thehydrocarbonylation process is especially useful for the production ofunsaturated alcohols, by hydroformylating alkadienes in the presence ofalpha olefins containing from 2 to 30, preferably 4 to 20, carbon atoms,including isobutylene, and internal olefins containing from 4 to 20carbon atoms as well as starting material mixtures of such alpha olefinsand internal olefins. Commercial alpha olefins containing four or morecarbon atoms may contain minor amounts of corresponding internal olefinsand/or their corresponding saturated hydrocarbon and that suchcommercial olefins need not necessarily be purified from same prior tobeing hydroformylated.

Illustrative of other olefinic starting materials include alpha-olefins,internal olefins, 1,3-dienes, 1,2-dienes, alkyl alkenoates, alkenylalkanoates, alkenyl alkyl ethers, alkenols, alkenals, and the like,e.g., ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 2-butene, 2-methyl propene (isobutylene), 2-methylbutene,2-pentene, 2-hexene, 3-hexane, 2-heptene, cyclohexene, propylene dimers,propylene trimers, propylene tetramers, piperylene, isoprene,2-ethyl-1-hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene,1,7-octadiene, 3-cyclohexyl-1-butene, allyl alcohol, allyl butyrate,hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenylacetate, vinyl propionate, allyl propionate, methyl methacrylate, vinylethyl ether, vinyl methyl ether, vinyl cyclohexene, allyl ethyl ether,methyl pentenoate n-propyl-7-octenoate, pentenals, e.g., 2-pentenal,3-pentenal and 4-pentenal; penten-1-ols, e.g., 2-penten-1-ol,3-penten-1-ol and 4-penten-1-ol; 3-butenenitrile, 3-pentenenitrile,5-hexenamide, 4-methyl styrene, 4-isopropyl styrene, 4-tert-butylstyrene, alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene,1,3-diisopropenylbenzene, eugenol, iso-eugenol, safrole, iso-safrole,anethol, 4-allylanisole, indene, limonene, beta-pine dicyclopentadiene,cyclooctadiene, camphene, linalool, and the like. Other illustrativeolefinic compounds may include, for example, p-isobutylstyrene,2-vinyl-6-methoxynaphthylene, 3-ethenylphenyl phenyl ketone,4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl,4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene,2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether,propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and thelike. Other olefinic compounds include substituted aryl ethylenes asdescribed in U.S. Pat. No. 4,329,507, the disclosure of which isincorporated herein by reference.

In those instances where the promoter is not the solvent, thehydrocarbonylation processes encompassed by this invention are conductedin the presence of an organic solvent for the metal-ligand complexcatalyst and free ligand. The solvent may also contain dissolved waterup to the saturation limit. Depending on the particular catalyst andreactants employed, suitable organic solvents include, for example,alcohols, alkanes, alkenes, alkynes, ethers, aldehydes, higher boilinghydrocarbonylation byproducts, ketones, esters, amides, tertiary amines,aromatics and the like. Any suitable solvent which does not undulyadversely interfere with the intended hydrocarbonylation reaction can beemployed. Mixtures of one or more different solvents may be employed ifdesired. Illustrative preferred solvents employable in the production ofalcohols include ketones (e.g. acetone and methylethyl ketone), esters(e.g. ethyl acetate), hydrocarbons (e.g. toluene), nitrohydrocarbons(e.g. nitrobenzene), ethers (e.g. tetrahydrofuran (THF) and sulfolane.Suitable solvents are disclosed in U.S. Pat. No. 5,312,996. The amountof solvent employed is not critical to the subject invention and needonly be that amount sufficient to solubilize the catalyst and freeligand of the hydrocarbonylation reaction mixture to be treated. Ingeneral, the amount of solvent may range from about 5 percent by weightup to about 99 percent by weight or more based on the total weight ofthe hydrocarbonylation reaction mixture starting material.

Illustrative substituted and unsubstituted unsaturated alcoholintermediates that can be prepared by the processes of this inventioninclude one or more of the following: alkenols such ascis-3-penten-1-ol, trans-3-penten-1-ol, 4-penten-1-ol, cis-2-penten-1-oland/or trans-2-penten-1-ol, including mixtures comprising one or more ofthe above unsaturated alcohols. Illustrative of suitable substituted andunsubstituted unsaturated alcohols (including derivatives of unsaturatedalcohols) include those permissible substituted and unsubstitutedunsaturated alcohols which are described in Kirk-Othmer, Encyclopedia ofChemical Technology, Fourth Edition, 1996, the pertinent portions ofwhich are incorporated herein by reference.

As indicated above, it is generally preferred to carry out thehydrocarbonylation stage or step in a continuous manner. In general,continuous hydrocarbonylation processes may involve: (a)hydrocarbonylating the alkadiene starting material(s) with carbonmonoxide and hydrogen in a liquid homogeneous reaction mixturecomprising a solvent, the metal-ligand complex catalyst, and freeligand; (b) maintaining reaction temperature and pressure conditionsfavorable to the hydrocarbonylation of the alkadiene startingmaterial(s); (c) supplying make-up quantities of the alkadiene startingmaterial(s), carbon monoxide and hydrogen to the reaction medium asthose reactants are used up; and (d) recovering the desired alcoholhydrocarbonylation product(s) in any manner desired. The continuousreaction can be carried out in a single pass mode, i.e., wherein avaporous mixture comprising unreacted alkadiene starting material(s) andvaporized alcohol product is removed from the liquid reaction mixturefrom whence the alcohol product is recovered and make-up alkadienestarting material(s), carbon monoxide and hydrogen are supplied to theliquid reaction medium for the next single pass through withoutrecycling the unreacted alkadiene starting material(s). However, it isgenerally desirable to employ a continuous reaction that involves eithera liquid and/or gas recycle procedure. Such types of recycle procedureare known in the art and may involve the liquid recycling of themetal-ligand complex catalyst solution separated from the desiredalcohol reaction product(s).

As indicated above, the hydrocarbonylation stage or step may involve aliquid catalyst recycle procedure. Such liquid catalyst recycleprocedures are known in the art. For instance, in such liquid catalystrecycle procedures it is commonplace to continuously or intermittentlyremove a portion of the liquid reaction product medium, containing,e.g., the alcohol product, the solubilized metal-ligand complexcatalyst, free ligand, and organic solvent, as well as byproductsproduced in situ by the hydrocarbonylation and unreacted alkadienestarting material, carbon monoxide and hydrogen (syn gas) dissolved insaid medium, from the hydrocarbonylation reactor, to a distillationzone, e.g., a vaporizer/separator wherein the desired alcohol product isdistilled in one or more stages under normal, reduced or elevatedpressure, as appropriate, and separated from the liquid medium. Thevaporized or distilled desired alcohol product so separated may then becondensed and recovered in any conventional manner as discussed above.The remaining non-volatilized liquid residue which contains metal-ligandcomplex catalyst, solvent, free ligand and usually some undistilledalcohol product is then recycled back, with or with out furthertreatment as desired, along with whatever by-product and non-volatilizedgaseous reactants that might still also be dissolved in said recycledliquid residue, in any conventional manner desired, to thehydrocarbonylation reactor, such as disclosed e.g., in theabove-mentioned patents. Moreover the reactant gases so removed by suchdistillation from the vaporizer may also be recycled back to the reactorif desired.

Recovery and purification of unsaturated alcohols may be by anyappropriate means, and may include distillation, phase separation,extraction, precipitation, absorption, crystallization, membraneseparation, derivative formation and other suitable means. For example,a crude reaction product can be subjected to a distillation-separationat atmospheric or reduced pressure through a packed distillation column.Reactive distillation may be useful in conducting the hydrocarbonylationreaction.

As indicated above, at the conclusion of (or during) thehydrocarbonylation process, the desired unsaturated alcohols, e.g.,penten-1-ols, may be recovered from the reaction mixtures used in theprocess of this invention. For instance, in a continuous liquid catalystrecycle reaction the portion of the liquid reaction mixture (containingpenten-1-ol product, catalyst, etc.) removed from the reactor can bepassed to a vaporizer/separator wherein the desired alcohol product canbe separated via distillation, in one or more stages, under normal,reduced or elevated pressure, from the liquid reaction solution,condensed and collected in a product receiver, and further purified ifdesired. The remaining non-volatilized catalyst containing liquidreaction mixture may then be recycled back to the reactor as may, ifdesired, any other volatile materials, e.g., unreacted alkadiene,together with any hydrogen and carbon monoxide dissolved in the liquidreaction after separation thereof from the condensed penten-1-olproduct, e.g., by distillation in any conventional manner. It isgenerally desirable to employ an organophosphorus ligand whose molecularweight exceeds that of the higher boiling alcohol oligomer byproductcorresponding to the penten-1-ols being produced in thehydrocarbonylation process. Another suitable recovery technique issolvent extraction or crystallization. In general, it is preferred toseparate the desired unsaturated alcohols from the catalyst-containingreaction mixture under reduced pressure and at low temperatures so as toavoid possible degradation of the organophosphorus ligand and reactionproducts. When an alpha-mono-olefin reactant is also employed, thealcohol derivative thereof can also be separated by the above methods.

More particularly, distillation and separation of the desired alcoholproduct from the metal-ligand complex catalyst containing productsolution may take place at any suitable temperature desired. In general,it is recommended that such distillation take place at relatively lowtemperatures, such as below 150° C., and more preferably at atemperature in the range of from about 50° C. to about 130° C. It isalso generally recommended that such alcohol distillation take placeunder reduced pressure, e.g., a total gas pressure that is substantiallylower than the total gas pressure employed during hydrocarbonylationwhen low boiling alcohols (e.g., C₅ and C₆) are involved or under vacuumwhen high boiling alcohols (e.g. C₇ or greater) are involved. Forinstance, a common practice is to subject the liquid reaction productmedium removed from the hydrocarbonylation reactor to a pressurereduction so as to volatilize a substantial portion of the unreactedgases dissolved in the liquid medium which now contains a much lowersynthesis gas concentration than was present in the hydrocarbonylationprocess medium to the distillation zone, e.g. vaporizer/separator,wherein the desired alcohol product is distilled. In general,distillation pressures ranging from vacuum pressures on up to total gaspressure of about 50 psig should be sufficient for most purposes.

While not wishing to be bound to any particular reaction mechanism, itis believed that the overall hydrocarbonylation reaction generallyproceeds in one step, i.e., the one or more substituted or unsubstitutedalkadienes (e.g., butadiene) are converted to one or more substituted orunsubstituted unsaturated alcohols (e.g., a 3-pentenol and/or4-pentenol) either directly or through one or more intermediates (e.g.,a 3-pentenal and/or 4-pentenal). This invention is not intended to belimited in any manner by any particular reaction mechanism, but ratherencompasses all permissible reaction mechanisms involved inhydrocarbonylating one or more substituted or unsubstituted alkadieneswith carbon monoxide and hydrogen in the presence of a metal-ligandcomplex catalyst and a promoter and optionally free ligand to produceone or more substituted or unsubstituted unsaturated alcohols.

As indicated above, the substituted and unsubstituted penten-1-olsproduced by the hydrocarbonylation step of this invention can beseparated by conventional techniques such as distillation, extraction,precipitation, crystallization, membrane separation, phase separation orother suitable means. For example, a crude reaction product can besubjected to a distillation-separation at atmospheric or reducedpressure through a packed distillation column. Reactive distillation maybe useful in conducting the hydrocarbonylation reaction step. Thesubsequent carbonylation of the penten-1-ols may be conducted withoutthe need to separate the penten-1-ols from the other components of thecrude reaction mixtures.

Carbonylation Step or Stage

The carbonylation step or stage of this invention involves convertingone or more substituted or unsubstituted penten-1-ols to one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. As used herein, the term “carbonylation” iscontemplated to include, but are not limited to, all permissiblecarbonylation processes, e.g., cyclocarbonylation, hydroxycarbonylationand alkoxycarbonylation, which involve converting one or moresubstituted or unsubstituted penten-1-ols to one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof. In general, the carbonylation step or stage comprises reactingone or more substituted or unsubstituted penten-1-ols with carbonmonoxide in the presence of a catalyst and optionally a promoter toproduce one or more substituted or unsubstituted epsilon caprolactones,e.g., cyclocarbonylation, and/or hydrates thereof, e.g.,hydroxycarbonylation, and/or esters thereof, e.g., alkoxycarbonylation.

The carbonylation processes of this invention may be conducted in one ormore steps or stages, preferably a one step process. The carbonylationreactions may be conducted in any permissible sequence so as to produceone or more substituted or unsubstituted epsilon caprolactones and/orhydrates and/or esters thereof.

While not wishing to be bound to any particular reaction mechanism, itis believed that the overall carbonylation reaction generally proceedsin one step, i.e., the one or more substituted or unsubstitutedpenten-1-ols are converted to one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof eitherdirectly or through one or more intermediates. This invention is notintended to be limited in any manner by any particular reactionmechanism, but rather encompasses all permissible carbonylationreactions which involve converting one or more substituted orunsubstituted penten-1-ols to one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof.

Suitable carbonylation reaction conditions and processing techniques andsuitable carbonylation catalysts include those described below. Thecarbonylation step or stage employed in the processes of this inventionmay be carried out as described below.

Penten-1-ols useful in the carbonylation are known materials and can beprepared as described above or by known methods. Reaction mixturescomprising penten-1-ols may be useful herein. The amounts ofpenten-1-ols employed in the carbonylation step is not narrowly criticaland can be any amounts sufficient to produce epsilon caprolactonesand/or hydrates and/or esters thereof, preferably in high selectivities.

The particular carbonylation reaction conditions are not narrowlycritical and can be any effective carbonylation conditions sufficient toproduce the epsilon caprolactones and/or hydrates and/or esters thereof.The reactors may be stirred tanks, tubular reactors and the like. Theexact reaction conditions will be governed by the best compromisebetween achieving high catalyst selectivity, activity, lifetime and easeof operability, as well as the intrinsic reactivity of the penten-1-olsin question and the stability of the penten-1-ols and the desiredreaction product to the reaction conditions. Illustrative of certainreaction conditions that may be employed in the carbonylation processesare described, for example, in U.S. Pat. No. 4,602,114, the disclosureof which is incorporated herein by reference. Products may be recoveredafter a particular reaction zone and purified if desired althoughpreferably they are introduced to the next reaction zone withoutpurification. Recovery and purification may be by any appropriate means,which will largely be determined by the particular penten-1-ol employed,and may include distillation, phase separation, extraction, absorption,crystallization, derivative formation and the like.

The catalysts useful in the carbonylation process include, for example,Group 6, 7, 8, 9 and 10 metal or metal complexes (supported orunsupported) in which suitable metals are selected from chromium (Cr),molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), rhodium(Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni),palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, withthe preferred metals being cobalt, rhodium, iridium, nickel andpalladium, more preferably cobalt, rhodium, iridium and palladium,especially palladium. Other catalysts useful in the carbonylationprocess include, for example, Group 6, 7, 8, 9 and 10 metal-ligandcomplex catalysts as described above. The carbonylation catalysts may bein homogeneous or heterogeneous form. Such catalysts may be prepared bymethods known in the art. This invention is not intended to be limitedin any manner by the permissible catalysts or mixtures thereof. Mixturesof catalysts may be employed if desired. It is to be noted that thesuccessful practice of this invention does not depend and is notpredicated on the exact structure of the catalyst species, which may bepresent in their mononuclear, dinuclear and/or higher nuclearity forms.Indeed, the exact structure is not known.

The permissible metals which make up the metal-ligand complex catalystsinclude Group 6, 7, 8, 9 and 10 metals selected from chromium (Cr),molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), rhodium(Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni),palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, withthe preferred metals being cobalt, rhodium, iridium, nickel andpalladium, more preferably cobalt, rhodium, iridium and palladium,especially palladium.

The permissible ligands include, for example, organophosphorus,organoarsenic and organoantimony ligands, or mixtures thereof,preferably organophosphorus ligands. The permissible organophosphorusligands which make up the metal-ligand complexes includeorganophosphines, e.g., mono-, di-, tri- and poly-(organophosphines),and organophosphites, e.g., mono-, di-, tri- andpoly-(organophosphites). Other permissible organophosphorus ligandsinclude, for example, organophosphonites, organophosphinites, aminophosphines and the like. Other permissible ligands which make up themetal-ligand complex catalyst include organonitrogen species, forexample, mono-, di-, tri-, and polyamines, mono-, di-, tri-, andpolyimines, mono-, di-, tri-, and polypyridines, andheteroatom-stabilized carbenes, e.g., mono-, di-, tri-, andpolycarbenes. Still other permissible ligands include, for example,heteroatom-containing ligands such as described in U.S. patentapplication Ser. No. 08/818,781, filed Mar. 10, 1997, the disclosure ofwhich is incorporated herein by reference. Mixtures of such ligands maybe employed if desired in the metal-ligand complex and/or free ligandand such mixtures may be the same or different. This invention is notintended to be limited in any manner by the permissible ligands ormixtures thereof. Illustrative of such organophosphorus ligands aredescribed above.

The catalysts useful in the carbonylation process may be promoted oractivated, for example, by acids, halides, quaternary ammonium orphosphonium halide salts, water, alcohols, hydrogen, nitrogen-containingcompounds or mixtures thereof. Permissible acids include Bronsted acidsand Lewis acids and mixtures thereof. The preferred Bronsted acidsinclude acids with pKa <7, e.g. carboxylic acids, sulfonic acids, HCland HI, and the preferred Lewis acids include metal halides, metalalkyls and metal aryls, e.g., SnCl₂, MgCl₂, BPh₃, AlCl₃, SnPh₂ andMgBu₂. Other permissible acids include hydrophosphoric acid,pyrophosphoric acid, phosphotungstic acid, molybdic acid, and mixturesthereof. Permissible halides include fluoride, chloride, bromide andiodide, e.g., methyl iodide, ethyl iodide, tetrabutylphosphonium iodideand tetrabutylammonium iodide. Permissible nitrogen-containing compoundsinclude N-heterocyclic bases, for example, pyridine, alkylatedpyridines, quinolines, lutidines, picolines, isoquinolines, alkylatedquinolines and isoquinolines, acridines and N-methyl-2-pyrrolidinone orN,N-dimethylaniline, N,N-diethylaniline, N,N-diethyltoluidine,N,N-dibutyltoluidine and N,N-dimethylformamide. The promoter may bepresent in the carbonylation reaction mixture either alone orincorporated into the ligand structure, either as the metal-ligandcomplex catalyst or as free ligand. The catalyst promoter should besufficient to generate an active catalytic species and to promoteremoval of product from the metal. The mole ratio of promoter to metalmay range from about 0.1:20 or less to about 20:1 or greater.

More particularly, illustrative metal-organophosphine complex catalystsand metal catalysts useful in the carbonylation process include, forexample, those disclosed in U.S. Pat. Nos. 4,602,114, 4,960,906,5,218,144, 5,420,346, 4,310,686, 4,692,549, 4,404,394, 4,670,582,4,786,443, 5,401,857, 4,634,780; European Patent Application Nos. 662467 and 329 252; and World Patent Application No. 9619427, thedisclosures of which are incorporated herein by reference.

In a preferred embodiment, the carbonylation reaction involvesconverting penten-1-ol in the liquid phase in the presence of carbonmonoxide, cobalt and pyridine to a reaction mixture comprising epsiloncaprolactones.

In another preferred embodiment, the carbonylation reaction involvesconverting penten-1-ol in the liquid phase in the presence of carbonmonoxide, palladium and a bidentate organic phosphorus, antimony orarsenic ligand to a reaction mixture comprising epsilon caprolactones.The bidentate ligand has as bridging group a bivalent organic compoundhaving at least 2 carbon atoms, preferably a bis(h-cyclopentadienyl)coordination group, of a transition metal. Preferably, iron is used as atransition metal in the metallocene compound (the bridging group being aferrocene). Preferably, phosphorus ligands are used because theseligands are more stable than the arsenic or antimony based ligands. Suchcarbonylation reactions are known in the art. See, for example, theabove U.S. Pat. No. 4,602,114.

Examples of suitable bidentate phosphine ligands according to theinvention are 1,1′-bis (diphenylphosphino)ferrocene;1,1′-bis(diisopropylphosphino)ferrocene;1,1′-bis(diisobutylphosphino)ferrocene;1,1′-bis(dipropylphosphino)ferrocene;1,1′-bis(dicyclohexylphosphino)ferrocene;1,1′-bis(isopropylcyclohexylphosphino)ferrocene;1,1′-bis(ditert-butylphosphino)ferrocene;1-(diisopropylphosphino)-1′-(phenylisopropylphosphino)ferrocene;1,1′-bis(di-2-thiophenylphosphino)ferrocene;1-(diisopropylphosphino)-1′-(diphenylphosphino)ferrocene;1,1′-bis(isopropylphenylphosphino)ferrocene; and1,1′-bis(di-2-thiophenylphosphino)ferrocene.

All solvents are in principle useful, but it is also possible to use anexcess of one of the reactants or byproducts in such an amount that asuitable liquid phase is formed. A possible suitable reactant is thepenten-1-ol and examples of byproducts are the high boiling byproducts.Examples of inert solvents are sulfoxides and sulfones, such as dimethylsulfoxide and diisopropyl sulfone; aromatic solvents such as benzene,toluene and xylene; esters such as methyl acetate, methyl valerate,pentenoate esters and butyrolactone; nitrites such as acetonitrile andbenzonitrile; ketones such as acetone or methylisobutyl ketone; andethers such as anisole, trioxanone, diphenyl ether and diisopropylether; and mixtures of these solvents.

The palladium may be present in the reaction mixture as a heterogeneouspalladium compound or as a homogeneous palladium compound. However,homogeneous systems are preferred. Since palladium in situ forms acomplex with the bidentate ligand, the choice of the initial palladiumcompound is in general not critical. Examples of homogeneous palladiumcompounds are palladium salts of, for example, nitric acid, sulfonicacid, alkane carboxylic acids with not more than 12 carbon atoms orhydrogen halogenides (F, Cl, Br, I), but metallic palladium may also beused. Examples of such palladium compounds are PdCl₂, PdBr₂, PdI₂,Na₂PdI₄, K₂PdI₄, PdCl₂ (benzonitrile)₂ and bis(allylpalladium chloride).Another group of suitable halogen-free palladium compounds are palladiumcomplexes such as palladium acetylacetonate (Pd(acac)₂), Pd(II) acetate,Pd(NO₃)₂, and palladium₂ (benzylidene acetone)₃. An example of asuitable heterogeneous palladium compound is palladium on an ionexchanger, such as for instance an ion exchanger containing sulfonicacid groups.

The bidentate ligand:palladium molar ratio is generally between about1:1 and 10:1. When this ratio is lower, palladium can precipitate,whereas when this ratio is higher, the catalytic effect is weaker andbyproducts such as high molecular weight products can form. The optimumratio will depend on the choice of the specific organic groups boundedto the phosphorus, arsenic or antimony atoms.

The carbonylation step is generally carried out at a temperature betweenabout 20° C. and 200° C. Preferably, the temperature is higher thanabout 50° C. and lower than about 160° C. The (initial) pressure ofcarbon monoxide and optionally hydrogen can generally be chosen from awide range, e.g., from about 1 to about 10,000 psia. Of course, it isunderstood that materials that generate carbon monoxide under reactionconditions may also be used, for example, formic acid, carbon dioxideand hydrogen. The total pressure employed in the carbonylation processmay range in general from about 20 to about 3000 psia, preferably fromabout 50 to 1500 psia.

When a complex of the ligand and palladium is separately prepared beforebeing added to the carbonylation reaction, an improved activity of thecatalyst and an improved selectivity to the desired epsilon caprolactonemay occur compared to the situation in which this complex may be formedin situ. Such a complex of palladium and ligand, hereinafter calledcatalyst precursor, can be prepared by mixing a palladium compound asdescribed above with the ligand. This mixing is preferably performed ina solvent. Temperature and pressure are not critical. The temperaturecan be, for example, between about 0° C. and 100° C. The pressure canbe, for example, atmospheric pressure. The mixing is preferablyperformed in the absence of air. Examples of possible solvents includeorganic solvents, for example, benzene, toluene, xylene, or aliphaticsolvents, for example, hexane, methyl pentenoate, methanol, acetone andethanol. Preferably the catalyst precursor is isolated from the mixtureby crystallization of the catalyst precursor under, for example,atmospheric pressure. The solid catalyst precursor can be separated fromthe solvent by, for example, filtration or evaporation of the solvent.The solid catalyst precursor is air stable and can be easily supplied tothe carbonylation reaction by, for example, dissolving the catalystprecursor in one of the reactants or solvents and supplying theresulting mixture to the reaction.

The carbonylation step may optionally be carried out in the presence ofa monodentate phosphine. The monodentate phosphine:bidentate ligandmolar ratio may range between about 1:10 and about 10:1.

In a preferred embodiment, this invention involves the preparation ofepsilon caprolactones by carbonylation of penten-1-ol as described abovewherein the following steps are performed:

(a) carbon monoxide, a source of palladium and the bidentate ligand andoptionally a protonic acid and a solvent are continuously brought into areactor in which the carbonylation takes place;

(b) continuously separating part of the reaction mixture from thereactor;

(c) separating from the separated reaction mixture unreacted carbonmonoxide and unreacted penten-1-ol and returning these reactants to step(a), and isolating the epsilon caprolactone; and

(d) returning the remaining mixture of step (c), containing palladiumand the bidentate ligand and optionally the solvent and the protonicacid, to step (a). Preferably a part of the remaining mixture of step(c) is separated from the mixture and led to a drain (purge) in order toprevent a build up of high boiling byproducts in the circulatingreaction mixture.

Step (a) can be performed in several ways, for example, in acontinuously stirred tank reactor or a bubble column in which theproduct is simultaneously stripped from the liquid phase.

Separating the carbon monoxide, penten-1-ol and the epsilon caprolactonefrom the reaction mixture in step (c) can be performed in various ways.Generally the carbon monoxide is separated first from the reactionmixture in, for example, a simple gas-liquid separation unit. Thepenten-1-ol and the epsilon caprolactone can be separated from thereaction mixture in one step followed by isolating the epsiloncaprolactone from penten-1-ol. Preferably the penten-1-ols are separatedfrom the reaction mixture in a separate step followed by the isolationof the epsilon caprolactone from the remaining reaction mixture.Separation of the various compounds can be performed in various ways,for example, by simple flash operation or by distillation. The choice asto which unit operation is the most suitable will depend on the physicalproperties of the compounds to be separated.

The ratio of the remaining mixture of step (c) which is returned to step(a) and the part which is processed to a drain will depend on the amountof contaminants (for example, high boiling byproducts) allowed in therecirculating reaction mixture. When a large part will be sent to thedrain, a low degree of contamination in the recirculating reactionmixture will be the result and vice versa. The ratio of the remainingmixture of step (c) which is returned to step (a) and the part which isprocessed to a drain will depend on the amount of contamination formedin the carbonylation step and the acceptable level of contamination inthe circulating process stream.

The part which is sent to the drain will contain apart from the abovementioned contaminants also the valuable palladium and ligand andoptionally acid and solvent (provided acid and solvent are used in thecarbonylation step). Preferably the palladium, bidentate ligand, acidand solvent will be isolated from this mixture in order toadvantageously reuse these compounds in the carbonylation step (step(a)). Examples of possible processes to separate these valuablecompounds from some of the byproducts is by distillation,crystallization and extraction.

The epsilon caprolactones and/or hydrates and/or esters thereof producedby the carbonylation step of this invention can be separated byconventional techniques such as distillation, extraction, precipitation,crystallization, membrane separation, phase separation or other suitablemeans. For example, a crude reaction product can be subjected to adistillation-separation at atmospheric or reduced pressure through apacked distillation column. Reactive distillation may be useful inconducting the carbonylation reaction step.

In the event that linear hydrates and/or esters of epsilon caprolactone,e.g., 6-hydroxyhexanoic acid and/or 6-hydroxyhexanoic acid esters, areformed, an optional cyclization process can be conducted which involvesconverting one or more substituted or unsubstituted 6-hydroxyhexanoicacids or one or more substituted or unsubstituted 6-hydroxyhexanoic acidesters to one or more substituted or unsubstituted epsilon caprolactonesin one or more steps or stages. As used herein, the term “cyclization”is contemplated to include all permissible cyclization processes whichinvolve converting one or more substituted or unsubstituted linearhydrates of epsilon caprolactone, e.g., 6-hydroxyhexanoic acids, or oneor more substituted or unsubstituted linear esters of epsiloncaprolactone, e.g., 6-hydroxyhexanoic acid esters, to one or moresubstituted or unsubstituted epsilon caprolactones. As used herein, theterm “epsilon caprolactone” is contemplated to include all permissiblesubstituted or unsubstituted epsilon caprolactones which may be derivedfrom one or more substituted or unsubstituted linear hydrates of epsiloncaprolactone, e.g., 6-hydroxyhexanoic acids, or one or more substitutedor unsubstituted linear esters of epsilon caprolactone, e.g.,6-hydroxyhexanoic acid esters.

6-Hydroxyhexanoic acids and 6-hydroxyhexanoic acid esters useful in thecyclization step are known materials and can be prepared as describedabove. Reaction mixtures comprising 6-hydroxyhexanoic acids and/or6-hydroxyhexanoic acid esters may be useful herein. The amounts of6-hydroxyhexanoic acids and 6-hydroxyhexanoic acid esters employed inthe cyclization step is not narrowly critical and can be any amountssufficient to produce epsilon caprolactones, preferably in highselectivities.

The cyclization reaction can be conducted at a temperature of from about0° C. to about 400° C. for a period of about 1 hour or less to about 4hours or longer with the longer time being used at the lowertemperature, preferably from about 50° C. to about 350° C. for about 1hour or less to about 2 hours or longer, and more preferably at about50° C. to about 200° C. for about 1 hour or less.

The cyclization reaction can be conducted over a wide range of pressuresranging from subatmospheric to about 3000 psig. It is preferable toconduct the cyclization reaction at pressures of from about 50 psig toabout 2500 psig. The cyclization reaction is preferably effected in theliquid or vapor states or mixtures thereof.

The amount of cyclization catalyst used is dependent on the particularcyclization catalyst employed and can range from about 0.01 weightpercent or less to about 10 weight percent or greater of the totalweight of the starting materials.

Such cyclization reactions may be performed in any appropriate solvent,under any appropriate atmosphere, or in the gas phase. Such solvents andatmospheres are chosen to allow the most desirable catalyst performance.For example, reactions may be performed under hydrogen gas in order tostabilize the catalyst from decomposition reactions to unproductivecatalysts. Suitable solvents include ethers, esters, lactones (such asepsilon caprolactone), ketones, aliphatic or aromatic hydrocarbons,fluorocarbons, silicones, polyethers, chlorinated hydrocarbons and thelike. The cyclization may be carried out using the pure epsiloncaprolactone precursor or the epsilon caprolactone precursor and amixture of byproducts from the earlier stages of the reaction sequence.If the transformation is carried out in the presence of water, it isdesirable that the solvent mixture employed be capable of dissolving allcomponents of the reaction mixture, except any heterogeneous catalyststhat may be employed.

The cyclization process may be carried out in one or more steps orstages and in any permissible sequence of steps or stages. In a one stepprocess, epsilon caprolactone is the major product leaving the reactionzone.

The particular cyclization reaction conditions are not narrowly criticaland can be any effective cyclization conditions sufficient to producethe epsilon caprolactone. The reactors may be stirred tanks, tubularreactors and the like. The exact reaction conditions will be governed bythe best compromise between achieving high catalyst selectivity,activity, lifetime and ease of operability, as well as the intrinsicreactivity of the epsilon caprolactone precursor in question and thestability of the epsilon caprolactone precursor and the desired reactionproduct to the reaction conditions. Products may be recovered after aparticular reaction zone and purified if desired although preferablythey are introduced to the next reaction zone without purification.Recovery and purification may be by any appropriate means, which willlargely be determined by the particular epsilon caprolactone precursoremployed, and may include distillation, phase separation, extraction,absorption, crystallization, derivative formation and the like.

The cyclization reaction of an epsilon caprolactone precursor may or maynot need a catalyst, depending on the particular epsilon caprolactoneprecursor employed. Although it may not be absolutely necessary toemploy a catalyst, it still may be desirable to do so to improve theselectivity or rate of the transformation. Other epsilon caprolactoneprecursors may necessitate the use of an appropriate catalyst. Since themechanism of the cyclization reaction depends on the epsiloncaprolactone precursor, the useful catalysts will be selected based uponthe epsilon caprolactone precursor employed.

A two phase system may also be used, providing adequate mixing isachieved. Such a system, however, may be used to facilitate recovery ofepsilon caprolactone after the cyclization reaction by extraction, phaseseparation or crystallization.

The epsilon caprolactones produced by the cyclization step of thisinvention can be separated by conventional techniques such asdistillation, extraction, precipitation, crystallization, membraneseparation, phase separation or other suitable means. For example, acrude reaction product can be subjected to a distillation-separation atatmospheric or reduced pressure through a packed distillation column.Reactive distillation may be useful in conducting the cyclizationreaction step.

As indicated herein, the processes of this invention may produce, inaddition to one or more substituted or unsubstituted epsiloncaprolactones, other desirable products, for example, hydrates ofepsilon caprolactones such as 6-hydroxyhexanoic acid, and esters such as6-hydroxyvaleric acid esters or esters thereof (e.g.,cis-3-pentenyl-6-hydroxyhexanoate, trans-3-pentenyl-6-hydroxyhexanoate,4-pentenyl-6-hydroxyhexanoate, poly(epsilon caprolactone)). Thisinvention is not intended to be limited in any manner by the permissibleproducts produced by the processes of this invention or the permissibleproducts contained in the reaction mixtures of this invention.

Illustrative epsilon caprolactones that can be prepared by the processesof this invention include epsilon caprolactone and substituted epsiloncaprolactones (e.g., alpha, beta, gamma and delta substituted epsiloncaprolactones). Illustrative of suitable substituted and unsubstitutedepsilon caprolactones (including derivatives of epsilon caprolactones)include those permissible substituted and unsubstituted epsiloncaprolactones which are described in Kirk-Othmer, Encyclopedia ofChemical Technology, Fourth Edition, 1996, the pertinent portions ofwhich are incorporated herein by reference.

Illustrative hydrates of epsilon caprolactones that can be prepared bythe processes of this invention include substituted or unsubstituted6-hydroxyhexanoic acids. Illustrative of suitable substituted andunsubstituted hydrates of epsilon caprolactones (including derivativesof epsilon caprolactones) include those permissible substituted andunsubstituted hydrates of epsilon caprolactones which may be describedin Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition,1996, the pertinent portions of which are incorporated herein byreference.

Illustrative esters that can be prepared by the processes of thisinvention include substituted or unsubstituted 6-hydroxyvaleric acidesters or esters thereof, e.g., cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone). Illustrative of suitable substituted andunsubstituted esters (including derivatives of such esters) includethose permissible substituted and unsubstituted esters which aredescribed in Kirk-Othmer, Encyclopedia of Chemical Technology, FourthEdition, 1996, the pertinent portions of which are incorporated hereinby reference.

The epsilon caprolactone, 6-hydroxyhexanoic acid and 6-hydroxyvalericacid ester products have a wide range of utilities that are well knownin the art, e.g., they are useful as starting materials/intermediates inthe production of epsilon caprolactam and polyesters. The6-hydroxyvaleric acid esters or esters thereof are also useful assolvents.

A process for producing epsilon caprolactones from one or moresubstituted or unsubstituted alkadienes is disclosed in copending U.S.patent application Ser. No. 60/043,342, filed Apr. 24, 1996, thedisclosure of which is incorporated herein by reference. Another processinvolving the reductive hydroformylation of one or more substituted orunsubstituted alkadienes to produce one or more substituted orunsubstituted penten-1-ols and carbonylation of the penten-1-ols toproduce epsilon caprolactones is disclosed in copending U.S. patentapplication Ser. No. 08/834,271, filed on an even date herewith, thedisclosure of which is incorporated herein by reference.

An embodiment of this invention relates to a process for producing oneor more substituted or unsubstituted epsilon caprolactones and/orhydrates and/or esters thereof which comprises:

(a) subjecting one or more substituted or unsubstituted alkadienes,e.g., butadiene, to hydrocarbonylation in the presence of ahydrocarbonylation catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, to produce one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols;

(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols from the hydrocarbonylation catalyst; and

(c) subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-olsto carbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. The reaction conditions in steps (a) and (c) maybe the same or different and the hydrocarbonylation and carbonylationcatalysts in steps (a) and (c) may be the same or different.

Yet another embodiment of this invention relates to a process forproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof which comprises:

(a) subjecting one or more substituted or unsubstituted alkadienes,e.g., butadiene, to hydrocarbonylation in the presence of ahydrocarbonylation catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, to produce one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols;

(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols from the hydrocarbonylation catalyst;

(c) optionally subjecting the 2-penten-1-ols and/or 3-penten-1-ols toisomerization in the presence of a heterogeneous or homogeneous olefinisomerization catalyst to partially or completely isomerize the2-penten-1-ols and/or 3-penten-1-ols to 3-penten-1-ols and/or4-penten-1-ol; and

(d) subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-olsto carbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. The reaction conditions in steps (a) and (d) maybe the same or different and the hydrocarbonylation and carbonylationcatalysts in steps (a) and (d) may be the same or different.

The olefin isomerization catalyst in step (c) may be any of a variety ofhomogeneous or heterogeneous transition metal-based catalysts(particularly Ni, Rh, Pd, Pt, Co, Ru, or Ir), or may be a heterogeneousor homogeneous acid catalyst (particularly any acidic zeolite, polymericresin, or source of H⁺, any of which may be modified with one or moretransition metals). Such olefin isomerization catalysts are known in theart and the isomerization can be conducted by conventional proceduresknown in the art. As used herein, the term “isomerization” iscontemplated to include, but are not limited to, all permissibleisomerization processes which involve converting one or more substitutedor unsubstituted 2-penten-1-ols and/or 3-penten-1-ols to one or moresubstituted or unsubstituted 4-penten-1-ols.

When the processes of this invention are conducted in two stages (i.e.,first producing 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-olsunder one set of conditions and then producing epsilon caprolactone fromthe 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-ols under anotherset of conditions), it is preferred to conduct the first stage at atemperature from 75° C. to 110° C. and at a total pressure from 250 psito 1000 psi and to conduct the second stage at a temperature from 60° C.to 120° C. and at a pressure from 5 psi to 500 psi. The same ordifferent catalysts can be used in the first and second stages. Theother conditions can be the same or different in both stages.

The processes of this invention can be operated over a wide range ofreaction rates (m/L/h=moles of product/liter of reaction solution/hour).Typically, the reaction rates are at least 0.01 m/L/h or higher,preferably at least 0.1 m/L/h or higher, and more preferably at least0.5 m/L/h or higher. Higher reaction rates are generally preferred froman economic standpoint, e.g., smaller reactor size, etc.

The processes of this invention may be carried out using, for example, afixed bed reactor, a fluid bed reactor, a continuous stirred tankreactor (CSTR) or a slurry reactor. The optimum size and shape of thecatalysts will depend on the type of reactor used. In general, for fluidbed reactors, a small, spherical catalyst particle is preferred for easyfluidization. With fixed bed reactors, larger catalyst particles arepreferred so the back pressure within the reactor is kept reasonablylow.

The processes of this invention can be conducted in a batch orcontinuous fashion, with recycle of unconsumed starting materials ifrequired. The reaction can be conducted in a single reaction zone or ina plurality of reaction zones, in series or in parallel or it may beconducted batchwise or continuously in an elongated tubular zone orseries of such zones. The materials of construction employed should beinert to the starting materials during the reaction and the fabricationof the equipment should be able to withstand the reaction temperaturesand pressures. Means to introduce and/or adjust the quantity of startingmaterials or ingredients introduced batchwise or continuously into thereaction zone during the course of the reaction can be convenientlyutilized in the processes especially to maintain the desired molar ratioof the starting materials. The reaction steps may be effected by theincremental addition of one of the starting materials to the other.Also, the reaction steps can be combined by the joint addition of thestarting materials. When complete conversion is not desired or notobtainable, the starting materials can be separated from the product,for example by distillation, and the starting materials then recycledback into the reaction zone.

The processes may be conducted in either glass lined, stainless steel orsimilar type reaction equipment. The reaction zone may be fitted withone or more internal and/or external heat exchanger(s) in order tocontrol undue temperature fluctuations, or to prevent any possible“runaway” reaction temperatures.

The processes of this invention may be conducted in one or more steps orstages. The exact number of reaction steps or stages will be governed bythe best compromise between achieving high catalyst selectivity,activity, lifetime and ease of operability, as well as the intrinsicreactivity of the starting materials in question and the stability ofthe starting materials and the desired reaction product to the reactionconditions.

In an embodiment, the processes useful in this invention may be carriedout in a multistaged reactor such as described, for example, incopending U.S. patent application Ser. No.08/757,743, filed on Nov. 26,1996, the disclosure of which is incorporated herein by reference. Suchmultistaged reactors can be designed with internal, physical barriersthat create more than one theoretical reactive stage per vessel. Ineffect, it is like having a number of reactors inside a singlecontinuous stirred tank reactor vessel. Multiple reactive stages withina single vessel is a cost effective way of using the reactor vesselvolume. It significantly reduces the number of vessels that otherwisewould be required to achieve the same results. Fewer vessels reduces theoverall capital required and maintenance concerns with separate vesselsand agitators.

The substituted and unsubstituted epsilon caprolactones and/or hydratesand/or esters produced by the processes of this invention can undergofurther reaction(s) to afford desired derivatives thereof. Suchpermissible derivatization reactions can be carried out in accordancewith conventional procedures known in the art. Illustrativederivatization reactions include, for example, hydrogenation,esterification, polymerization, copolymerization, etherification,amination, alkylation, dehydrogenation, reduction, acylation,cyclization, hydration, neutralization, condensation, carboxylation,carbonylation, oxidation, silylation and the like, including permissiblecombinations thereof. This invention is not intended to be limited inany manner by the permissible derivatization reactions or permissiblederivatives of substituted and unsubstituted epsilon caprolactonesand/or hydrates and/or esters.

For purposes of this invention, the term “hydrocarbon” is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. Such permissible compounds may also have one or moreheteroatoms. In a broad aspect, the permissible hydrocarbons includeacyclic (with or without heteroatoms) and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds which can be substituted or unsubstituted.

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements reproduced in “BasicInorganic Chemistry” by F. Albert Cotton, Geoffrey Wilkinson and Paul L.Gaus, published by John Wiley and Sons, Inc., 3rd Edition, 1995.

Certain of the following examples are provided to further illustratethis invention.

EXAMPLES 1-19

Into a 100 milliliter overhead stirred high pressure reactor was charged0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol of atrialkylphosphine defined in Table A below, 3 milliliters of butadiene,26 milliliters of a solvent as defined in Table A, and 1 milliliter ofdiglyme as internal standard. The reactor was pressurized with 5-10 psiof hydrogen/carbon monoxide in 1/1 ratio and heated to the desiredtemperature set out in Table A. At the desired temperature, the reactorwas pressurized to the desired hydrogen/carbon monoxide ratio set out inTable A and the gas uptake was monitored. After a decrease in pressureof 10%, the reactor was re-pressurized to the initial value withhydrogen/carbon monoxide in 1/1 ratio. Samples of the reaction mixturewere taken in dry ice cooled vials via the sampling line at scheduledintervals and analyzed by gas chromatography. At the end of the reactionperiod of 90 minutes, the gases were vented and the reaction mixturedrained. Further details and results of analyses are set out in Table A.

TABLE A Ex. Temp. H₂/CO Butadiene Rate Selectivity (%) No.Solvent/Promoter Phosphine (° C.) (psi) Conv. (%) m/L/h 3 & 4 Pentenols 1 Ethanol Triethylphosphine 60 300/300 27 0.2 92  2 EthanolTriethylphosphine 80 300/300 90 1.6 87  3 Ethanol Triethylphosphine 80500/500 87 1.3 91  4 Ethanol Triethylphosphine 80 75/75 75 0.3 71  5Octanol Trioctylphosphine 80 600/200 98 1.9 88  6 3-PentenolTrioctylphosphine 80 600/200 89 nd 90  7 Hexanediol Trioctylphosphine 80300/300 65 nd 93  8 Pyrrole Trioctylphosphine 80 600/200 90 1.4 88  9Ethanol Tributylphosphine 80 300/300 55 1.0 70 10 Phenol/THFTrioctylphosphine 80 600/200 84 2.0 55 11 t-Butanol Triethylphosphine120  250/250 99 nd 38 (15 min rxn. time) 12 Ethanol Trimethylphosphine120  250/250 97 nd 42 (2 h rxn. time) 13 EthanolDiethyl-para-N,N-dimethylphenylphosphine 80 600/200 70 1.2 64 14Ethanol/Acetonitrile Triethylphosphine 80 300/300 68 1.1 82 15Ethanol/Tetraglyme Triethylphosphine 80 300/300 64 1.0 91 16Diphenylamine Trioctylphosphine 80 600/200 80 0.8 54 17 AcetamideTrioctylphosphine 80 600/200 85 0.9 34 18 MethylacetamideTrioctylphosphine 80 600/200 73 0.8 59 19 N-MethylformamideTrioctylphosphine 80 600/200 33 0.1 19 nd = not determined

EXAMPLES 20-26

Into a 100 milliliter overhead stirred high pressure reactor as charged0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol of atrialkylphosphine defined in Table B below, 3 milliliters of butadiene,26 milliliters of ethanol, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 5-10 psi of hydrogen/carbonmonoxide in 1/1 ratio and heated to 80° C. At the desired temperature,the reactor was pressurized to the desired hydrogen/carbon monoxideratio set out in Table B and the gas uptake was monitored. After adecrease in pressure of 10%, the reactor was re-pressurized to theinitial value with hydrogen/carbon monoxide in 1/1 ratio. Samples of thereaction mixture were taken in dry ice cooled vials via the samplingline at scheduled intervals and analyzed by gas chromatography. At theend of the reaction period of 120 minutes, the gases were vented and thereaction mixture drained. Further details and results of analyses areset out in Table B.

TABLE B Buta diene Ex. H₂/CO Conv Rate Selectivity (%) No. Phosphine(psi) (%) (m/L/h) 3 & 4 Pentenols 20 t-butyldiethyl 300/300 60 0.8 13phosphine 21 t-butyldiethyl 800/200 69 1.1 19 phosphine 22cyclohexyldiethyl 300/300 76 0.7 75 phosphine 23 cyclohexyldiethyl800/200 82 1.4 80 phosphine 24 n-butyldiethyl 300/300 77 1.1 82phosphine 25 diethylphenyl 200/800 53 0.9 77 phosphine 26 ethyldiphenyl200/800 38 0.6 27 phosphine

EXAMPLE 27

A 160 milliliter magnetically stirred autoclave was purged with 1:1H₂/CO and charged with a catalyst solution consisting of 0.1125 grams(0.44 mmol) dicarbonylacetylacetonato rhodium (I), 0.3515 grams (2.94mmol) P(CH₂CH₂CH₂OH)₃, and 44.1 grams tetrahydrofuran. The autoclave waspressurized with 40 psig 1:1 H₂/CO and heated to 80° C. 6 milliliters(3.73 grams) of 1,3-butadiene was charged with a metering pump and thereactor was pressurized to 1000 psig with 1:1 H₂/CO. The reactionmixture was maintained at 80° C. under 1000 psi 1:1 H₂/CO. Samples ofthe reaction mixture taken after 90 minutes and 170 minutes provided theresults set out in Table

TABLE C Tempera- Butadiene Selectivity (%) Time ture H₂/CO ConversionRate 3 & 4 (minutes) (° C.) (psig) (%) (m/L/h) Pentenols 90 80 500/50081 0.7 66 170 80 500/500 96 0.4 72

EXAMPLE 28

A 160 milliliter magnetically stirred autoclave was purged with 1:1H₂/CO and charged with a catalyst solution consisting of 0.1126 grams(0.44 mmol) dicarbonylacetylacetonato rhodium (I), 0.6120 grams (1.69mmol) P(CH₂CH₂CH₂OH)₃, and 39.9 grams of ethanol. The autoclave waspressurized with 40 psig 1:1 H₂/CO and heated to 80° C. 6 milliliters(3.73 grams) of 1,3-butadiene was charged with a metering pump and thereactor pressurized to 1000 psig with 1:1 H₂/CO. The reaction mixturewas maintained at 80° C. under 1000 psi 1:1 H₂/CO. Samples of thereaction mixture taken after 15 and 43 minutes provided the results inTable D below.

TABLE D Tempera- Butadiene Selectivity (%) Time ture H₂/CO ConversionRate 3 & 4 (minutes) (° C.) (psig) (%) (m/L/h) Pentenols 15 80 500/50053 2.6 70 43 80 500/500 89 1.5 78

EXAMPLE 29

A 100 milliliter overhead stirred high pressure reactor was charged with0.17 mmol bis(triphenylphosphine)palladium(II) dichloride, 0.86 mmoltin(II) dichloride, 1.5 milliliters of cis-3-pentenol, 26 milliliters ofmethyl isobutyl ketone, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 10 psi carbon monoxide,heated to 100° C., and then pressurized to 1600 psi carbon monoxide.Samples of the reaction mixture were taken at time zero and after 2.5hours, and then analyzed by gas chromatography. At the end of thereaction (2.5 hours), the gases were vented and the reaction mixturedrained. Details of the reaction are set out in Table E below.

EXAMPLE 30

A 100 milliliter overhead stirred high pressure reactor was charged with0.27 mmol bis(triphenylphosphine)palladium(II) dichloride, 0.55 mmoltriphenylphosphine, 2.7 mmol hydrogen chloride, 2 milliliters of water,1.5 milliliters of 3-pentenol, 24 milliliters of 1,4-dioxane, and 1milliliter of diglyme as internal standard. The reactor was pressurizedwith 10 psi carbon monoxide, heated to 130° C., and then pressurized to1300 psi carbon monoxide. Samples of the reaction mixture were taken attime zero and after 2 hours, and then analyzed by gas chromatography. Atthe end of the reaction (2 hours), the gases were vented and thereaction mixture drained. Details of the reaction are set out in TableE.

EXAMPLE 31

A 100 milliliter overhead stirred high pressure reactor was charged with0.27 mmol palladium(II) acetate, 0.54 mmolbis(diphenylphosphino)ferrocene, 2.7 mmol methane sulfonic acid, 2milliliters of water, 1.5 milliliters of 3-pentenol, 24 milliliters of1,4-dioxane, and 1 milliliter of diglyme as internal standard. Thereactor was pressurized with 10 psi carbon monoxide, heated to 130° C.,and then pressurized to 600 psi carbon monoxide. Samples of the reactionmixture were taken at time zero and after 2.5 hours, and then analyzedby gas chromatography. At the end of the reaction (2.5 hours), the gaseswere vented and the reaction mixture drained. Details of the reactionare set out in Table E.

EXAMPLE 32

A 100 milliliter overhead stirred high pressure reactor was charged with0.28 mmol palladium(II) acetate, 0.55 mmol ofbis(2,2′-diphenylphosphinomethyl)biphenyl, 2.7 mmol methane sulfonicacid, 2 milliliters of water, 1.5 milliliters of 3-pentenol, 24milliliters of 1,4-dioxane, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 10 psi carbon monoxide,heated to 130° C., and then pressurized to 1500 psi carbon monoxide.Samples of the reaction mixture were taken at time zero and after 2hours, and then analyzed by gas chromatography. At the end of thereaction (2 hours), the gases were vented and the reaction mixturedrained. Details of the reaction are set out in Table E.

EXAMPLE 33

A 100 milliliter overhead stirred high pressure reactor was charged with0.76 mmol dicobalt octacarbonyl, 3.3 mmol pyridine, 1.5 milliliters ofcis-3-pentenol, 26 milliliters of acetonitrile, and 1 milliliter ofdiglyme as internal standard. The reactor was pressurized with 10 psicarbon monoxide, heated to 160° C., and then pressurized to 1900 psicarbon monoxide. Samples of the reaction mixture were taken at time zeroand after 2 hours, and then analyzed by gas chromatography. At the endof the reaction (2.5 hours), the gases were vented and the reactionmixture drained. Details of the reaction are set out in Table E.

EXAMPLE 34

A 100 milliliter overhead stirred high pressure reactor was charged with0.25 mmol palladium(II) acetate, 0.63 mmol mmol1,2-bis(1,5-cyclooctylenephosphino)ethane, 0.26 mmol tin(II) dichloride,3 milliliters of 4-pentenol, 26 milliliters of methyl isobutyl ketone,and 1 milliliter of diglyme as internal standard. The reactor waspressurized with 10 psi carbon monoxide and hydrogen, heated to 100° C.,and then pressurized to 600 psi carbon monoxide and hydrogen. Samples ofthe reaction mixture were taken at time zero and after 2 hours, and thenanalyzed by gas chromatography. At the end of the reaction (2 hours),the gases were vented and the reaction mixture drained. Details of thereaction are set out in Table E.

EXAMPLE 35

A 100 milliliter overhead stirred high pressure reactor was charged with0.18 mmol bis(triphenylphosphine)palladium(II) dichloride, 0.87 mmoltin(II) dichloride, 3 milliliters of 4-pentenol, 26 milliliters ofmethyl isobutyl ketone, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 10 psi carbon monoxide,heated to 100° C., and then pressurized to 1600 psi carbon monoxide.Samples of the reaction mixture were taken at time zero and after 2.5hours, and then analyzed by gas chromatography. At the end of thereaction (2.5 hours), the gases were vented and the reaction mixturedrained. Details of the reaction are set out in Table E.

EXAMPLE 36

A 100 milliliter overhead stirred high pressure reactor was charged with0.24 mmol palladium(II) acetate, 0.62 mmol1,2-bis(1,5-cyclooctylenephosphino)ethane, 3 milliliters of 4-pentenol,26 milliliters of toluene, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 10 psi carbon monoxide andhydrogen, heated to 100° C., and then pressurized to 600 psi carbonmonoxide and hydrogen. Samples of the reaction mixture were taken attime zero and after 2.5 hours, and then analyzed by gas chromatography.At the end of the reaction (2.5 hours), the gases were vented and thereaction mixture drained. Details of the reaction are set out in TableE.

EXAMPLE 37

A 100 milliliter overhead stirred high pressure reactor was charged with0.26 mmol palladium(II) acetate, 0.64 mmol1,2-bis(1,5-cyclooctylenephosphino)ethane, 3 milliliters of 4-pentenol,26 milliliters of tetrahydrofuran, and 1 milliliter of diglyme asinternal standard. The reactor was pressurized with 10 psi carbonmonoxide and hydrogen, heated to 100° C., and then pressurized to 600psi carbon monoxide and hydrogen. Samples of the reaction mixture weretaken at time zero and after 2.5 hours, and then analyzed by gaschromatography. At the end of the reaction (2.5 hours), the gases werevented and the reaction mixture drained. Details of the reaction are setout in Table E.

TABLE E Pent. Ex. Temp. CO/H₂ Con. Rate C5 Et5L Me6L Cap Ester No. MetalLigand Promoter Solvent (° C.) (psi) (%) (M/l − h) (%) (%) (%) (%) (%)29 Pd TPP SnCl₂ MIBK 100 1600/0 15 0.06 30 25 1 30 Pd TPP HCl DIOX 1301300/0 32 0.08 29 39 5 31 Pd DPPF MSA DIOX 130  600/0 46 0.10 15 31 20 132 Pd BISBI MSA DIOX 130 1500/0 63 0.15 38 60 1 33 Co py py ACTN 1601900/0 22 0.06 45 32 15 7 34 Pd BCPE SnCl₂ MIBK 100   300/300 66 0.31 73 2  7 12   5 35 Pd TPP SnCl₂ MIBK 100 1600/0 77 0.35 10 12 18 49  11 36Pd BCPE PhMe 100   300/300 51 0.03 32  1  5 12  48 37 Pd BCPE THF 100  300/300 89 0.27 68  5  6 12   8 Pent. Conv. (Ex. 29-33) = 3-pentenolconversion; Pent. Conv. (Ex. 34-37) = 4-pentenol conversion; C5 (Ex.29-33) = 1-pentanol + valeraldehyde; C5 (Ex. 34-37) = 3-pentenol; Et5L =2-ethylbutyrolacetone; Me6L = 2-methylvalerolactone; Cap =ε-caprolactone; Ester = 4-pentenyl-6-hydroxyhexanoate +3-pentenyl-6-hydroxyhexanoate; TPP = triphenylphosphine; DPPF =1,1′-bis(diphenylphosphino)ferrocene; BISBI =bis(2,2′-diphenylphosphinomethyl)biphenyl; py = pyridine; BCPE =1,2-bis(1,5-cyclooctylenephosphino)ethane; MSA = methane sulfonic acid;MIBK = methyl isobutyl ketone; DIOX = 1,4-dioxane; ACTN = acetonitrile;PhMe = toluene; THF = tetrahydrofuran.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for producing one or more substitutedor unsubstituted epsilon caprolactones and/or hydrates and/or estersthereof which comprises: (a) subjecting one or more substituted orunsubstituted alkadienes to hydrocarbonylation in the presence of ahydrocarbonylation catalyst and a promoter to produce one or moresubstituted or unsubstituted penten-1-ols comprising 3-penten-1-ols,wherein said promoter comprises an organic or inorganic compound with anionizable hydrogen of pKa of from about 1 to about 35; and (b)subjecting said one or more substituted or unsubstituted penten-1-ols toisomerization and carbonylation in the presence of an isomerization andcarbonylation catalyst to produce said one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof.
 2. The process of claim 1 wherein the substituted orunsubstituted alkadiene comprises butadiene, the substituted orunsubstituted penten-1-ols comprise cis-3-penten-1-ol,trans-3-penten-1-ol, 4-penten-1-ol, cis-2-penten-1-ol and/ortrans-2-penten-1-ol, and the substituted or unsubstituted epsiloncaprolactone and/or hydrates and/or esters thereof comprises epsiloncaprolactone and/or 6-hydroxyhexanoic acid.
 3. The process of claim 1wherein said hydrocarbonylation catalyst comprises a metal selected froma Group 8, 9 and 10 metal complexed with an organophosphine ligandselected from a mono-, di-, tri- and poly-(organophosphine) ligand. 4.The process of claim 1 wherein said hydrocarbonylation catalystcomprises a metal selected from a Group 8, 9 and 10 metal complexed withan organophosphine ligand selected from a triorganophosphine ligandrepresented by the formula:

wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical.
 5. The process of claim 4wherein each R¹ is the same or different and is selected from primaryalkyl, secondary alkyl, tertiary alkyl and aryl.
 6. The process of claim3 wherein the organophosphine ligand has a basicity greater than orequal to the basicity of triphenylphosphine (pKb=2.74) and a steric bulklower than or equal to a Tolman cone angle of 210°.
 7. The process ofclaim 3 wherein said promoter is incorporated into the organophosphineligand structure either as the metal-organophosphine ligand complexcatalyst or as free organophosphine ligand.
 8. The process of claim 3wherein said promoter comprises a protic solvent, organic and inorganicacid, alcohol, water, phenol, thiol, selenol, nitroalkane, ketone,nitrile, amine, amide, or a mono-, di- or trialkylammonium salt ormixtures thereof.
 9. The process of claim 1 wherein the carbonylationcatalyst comprises a metal-ligand complex catalyst.
 10. The process ofclaim 9 wherein said metal-ligand complex catalyst comprises a metalselected from a Group 8, 9 and 10 metal complexed with anorganophosphorus ligand selected from a mono-, di-, tri- andpoly-(organophosphine) ligand.
 11. The process of claim 1 wherein saidhydrocarbonylation catalyst comprises a metal selected from a Group 8, 9and 10 metal complexed with an organophosphorus ligand selected from:(i) a triorganophosphine ligand represented by the formula:

wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical; (ii) a monoorganophosphiterepresented by the formula:

wherein R³ represents a substituted or unsubstituted trivalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater;(iii) a diorganophosphite represented by the formula:

wherein R⁴ represents a substituted or unsubstituted divalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater andW represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 18 carbon atoms or greater; (iv) atriorganophosphite represented by the formula:

wherein each R⁸ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical; and (v) anorganopolyphosphite containing two or more tertiary (trivalent)phosphorus atoms represented by the formula:

wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and is a divalent hydrocarbon radicalcontaining from 4 to 40 carbon atoms, each R¹⁰ is the same or differentand is a substituted or unsubstituted monovalent hydrocarbon radicalcontaining from 1 to 24 carbon atoms, a and b can be the same ordifferent and each have a value of 0 to 6, with the proviso that the sumof a+b is 2 to 6 and n equals a+b.
 12. The process of claim 1 whereinthe carbonylation catalyst comprises cobalt carbonyl.
 13. The process ofclaim 1 wherein the carbonylation catalyst comprises apalladium-organophosphorus ligand complex catalyst.
 14. The process ofclaim 1 wherein the carbonylation catalyst comprises ametal-organophosphorus ligand complex catalyst which is activated by apromoter comprising a metal halide or acid.
 15. The process of claim 1which is conducted at a temperature from about 50° C. to 150° C. and ata total pressure from about 20 psig to about 3000 psig.
 16. A processfor selectively producing one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof whichcomprises: (a) subjecting one or more substituted or unsubstitutedalkadienes to hydrocarbonylation in the presence of a hydrocarbonylationcatalyst and a promoter to produce one or more substituted orunsubstituted unsaturated alcohols comprising 3-penten-1-ols, whereinsaid promoter comprises an organic or inorganic compound with anionizable hydrogen of pKa of from about 1 to about 35; (b) separatingthe 3-penten-1-ols from the hydrocarbonylation catalyst; and (c)subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols to isomerization and carbonylation inthe presence of an isomerization and carbonylation catalyst to producesaid one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof.
 17. A process for selectivelyproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof which comprises: (a) subjectingone or more substituted or unsubstituted alkadienes tohydrocarbonylation in the presence of a hydrocarbonylation catalyst anda promoter to produce one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, wherein said promotercomprises an organic or inorganic compound with an ionizable hydrogen ofpKa of from about 1 to about 35; and (b) optionally separating the3-penten-1-ols from the hydrocarbonylation catalyst; (c) subjecting the3-penten-1-ols to isomerization in the presence of a heterogeneous orhomogeneous olefin isomerization catalyst to partially or completelyisomerize the 3-penten-1-ols to 4-penten-1-ol; and (d) subjecting saidone or more substituted or unsubstituted unsaturated alcohols comprising4-penten-1-ol to carbonylation in the presence of a carbonylationcatalyst to produce said one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof.